Vivianite and siderite in lateritic iron crust: an example of bioreduction

Lateritic iron crust (LIC) samples from Padauari (AM) were analysed by XRD, optical microscopy and SEM-EDS. The equilibrium of iron minerals (IM) was studied using Eh-pH diagram. It was shown that the minerals of the LIC are goethite (alpha-FeOOH), vivianite [Fe3(PO4)2.8H2O] and siderite (FeCO3). Carbonate grains are a solid solution of FeCO3-MnCO3. The LIC presents textures and structures of dissolution of IM. The siderite and vivianite are stable from Eh =-0.3 to 0.0 V and pH=5.0-7.5. These results indicate that vivianite and siderite are products of bioreduction through biogenic dissolution of IM, the new conditions of ecosystems of the Amazon region.

Vivianite and siderite in lateritic iron crust: an example of bioreduction

Lateritic iron crust (LIC) samples from Padauari (AM) were analysed by XRD, optical microscopy and SEM-EDS. The equilibrium of iron minerals (IM) was studied using Eh-pH diagram. It was shown that the minerals of the LIC are goethite (a-FeOOH), vivianite [Fe₃(PO₄)₂.8H₂O] and siderite (FeCO₃). Carbonate grains are a solid solution of FeCO₃-MnCO₃. The LIC presents textures and structures of dissolution of IM. The siderite and vivianite are stable from Eh =-0.3 to 0.0 V and pH=5.0-7.5. These results indicate that vivianite and siderite are products of bioreduction through biogenic dissolution of IM, the new conditions of ecosystems of the Amazon region.

"Brienzi" - The blue Vivianite man of Switzerland: Time since death estimation of an adipocere body

In 1996, a cadaver in adipocere condition was discovered in a bay of the Brienzer See in Switzerland. The torso was named "Brienzi" following the "Iceman" Ötzi. Several outer parts of the body were incrusted; the incrustation was in blue color. Further investigations showed that the bluish covering of parts of the adipocere torso were a mineral known as Vivianite. Vivianite (Fe(3)(PO(4))(2-)(H(2)O)(8)) is an iron phosphate mineral with needle lengths between 100 and 150μm. It is normally associated in a context with organic archaeological and geological materials (some hundreds to millions of years old). Hitherto, it is only described in three cases of human remains. We were able to reconstruct the following facts about 'Brienzi': The man drowned in Lake Brienz or in one of its tributaries during the 1700s. The body was subsequently covered with sedimentation and thus buried under water. An earthquake produced an underwater landslide which eventually exposed the corpse.

The significance of vivianite in archaeological settings

Vivianite is a bluish mineral sometimes encountered in archaeological deposits. It is notable for its tendency to change color from white or grayish to blue on exposure to air. Vivianite requires specific conditions for its formation-sources of iron, phosphate, and water, as well as low levels of oxygen and sulfide. Microbial activity is also thought to play a part in vivianite formation. The majority of archaeological texts do not discuss vivianite to any great degree, preventing a more detailed interpretation of site conditions and features. Vivianite was found in 25 exhumed burials from the North Brisbane Burial Ground, Queensland, Australia. Research indicated that bone or tissue samples for DNA analysis are best taken from areas distant from vivianite encrustations and that presence of vivianite has implications for artifact conservation. Vivianite at the North Brisbane Burial Grounds helped protect some skeletal and dental elements, preserved the impressions of metal coffin lacing, and also corroborated the oral history of temporary waterlogging and acted as a measure of pollution levels across the site. (c) 2006 Wiley Periodicals, Inc.

Geochemistry and mineralogy of Eocene-Oligocene sediments of IODP Hole 302-M0002A

In 2004, Integrated Ocean Drilling Program Expedition 302 (Arctic Coring Expedition, ACEX) to the Lomonosov Ridge drilled the first Central Arctic Ocean sediment record reaching the uppermost Cretaceous (~430 m composite depth). While the Neogene part of the record is characterized by grayish-yellowish siliciclastic material, the Paleogene part is dominated by biosiliceous black shale-type sediments. The lithological transition between Paleogene and Neogene deposits was initially interpreted as a single sedimentological unconformity (hiatus) of ~26 Ma duration, separating Eocene from Miocene strata. More recently, however, continuous sedimentation on Lomonosov Ridge throughout the Cenozoic was proclaimed, questioning the existence of a hiatus. In this context, we studied the elemental and mineralogical sediment composition around the Paleogene-Neogene transition at high resolution to reconstruct variations in the depositional regime (e.g. wave/current activity, detrital provenance, and bottom water redox conditions). Already below the hiatus, mineralogical and geochemical proxies imply drastic changes in sediment provenance and/or weathering intensity in the hinterland, and point to the existence of another, earlier gap in the sediment record. The sediments directly overlying the hiatus (the Zebra interval) are characterized by pronounced and abrupt compositional changes that suggest repeated erosion and re-deposition of material. Regarding redox conditions, euxinic bottom waters prevailed at the Eocene Lomonosov Ridge, and became even more severe directly before the hiatus. With detrital sedimentation rates decreasing, authigenic trace metals were highly enriched in the sediment. This continuous authigenic trace metal enrichment under persistent euxinia implies that the Arctic trace metal pool was renewed continuously by water mass exchange with the world ocean, so the Eocene Arctic Ocean was not fully restricted. Above the hiatus, extreme positive Ce anomalies are clear signs of a periodically well-oxygenated water column, but redox conditions were highly variable during deposition of the Zebra interval. Significant Mn enrichments only occur above the Zebra interval, documenting the Miocene establishment of stable oxic conditions in the Arctic Ocean. In summary, extreme and abrupt changes in geochemistry and mineralogy across the studied sediment section do not suggest continuous sedimentation at the Lomonosov Ridge around the Eocene-Miocene transition, but imply repeated periods of very low sedimentation rates and/or erosion.

Results of bulk sediment X-ray diffraction analysis and quantification of mineral phases based on the RockJock and on the QUAX quantitative analysis

We have performed quantitative X-ray diffraction (qXRD) analysis of 157 grab or core-top samples from the western Nordic Seas between (WNS) ~57°-75°N and 5° to 45° W. The RockJock Vs6 analysis includes non-clay (20) and clay (10) mineral species in the <2 mm size fraction that sum to 100 weight %. The data matrix was reduced to 9 and 6 variables respectively by excluding minerals with low weight% and by grouping into larger groups, such as the alkali and plagioclase feldspars. Because of its potential dual origins calcite was placed outside of the sum. We initially hypothesized that a combination of regional bedrock outcrops and transport associated with drift-ice, meltwater plumes, and bottom currents would result in 6 clusters defined by "similar" mineral compositions. The hypothesis was tested by use of a fuzzy k-mean clustering algorithm and key minerals were identified by step-wise Discriminant Function Analysis. Key minerals in defining the clusters include quartz, pyroxene, muscovite, and amphibole. With 5 clusters, 87.5% of the observations are correctly classified. The geographic distributions of the five k-mean clusters compares reasonably well with the original hypothesis. The close spatial relationship between bedrock geology and discrete cluster membership stresses the importance of this variable at both the WNS-scale and at a more local scale in NE Greenland.

Solid phase analysis of sediment core GeoB9309-1 from the Zambezi (or Mozambique) deep-sea fan

The Zambezi deep-sea fan, the largest of its kind along the east African continental margin, is poorly studied to date, despite its potential to record marine and terrestrial climate signals in the southwest Indian Ocean. Therefore, gravity core GeoB 9309-1, retrieved from 1219 m water depth, was investigated for various geophysical (magnetic susceptibility, porosity, colour reflectance) and geochemical (pore water and sediment geochemistry, Fe and P speciation) properties. Onboard and onshore data documented a sulphate/methane transition (SMT) zone at ~ 450-530 cm sediment depth, where the simultaneous consumption of pore water sulphate and methane liberates hydrogen sulphide and bi-carbonate into the pore space. This leads to characteristic changes in the sediment and pore water chemistry, as the reduction of primary Fe (oxyhydr)oxides, the precipitation of Fe sulphides, and the mobilization of Fe (oxyhydr)oxide-bound P. These chemical processes also lead to a marked decrease in magnetic susceptibility. Below the SMT, we find a reduction of porosity, possibly due to pore space cementation by authigenic minerals. Formation of the observed geochemical, magnetic and mineralogical patterns requires a fixation of the SMT at this distinct sediment depth for a considerable time-which we calculated to be ~ 10 000 years assuming steady-state conditions-following a period of rapid upward migration towards this interval. We postulate that the worldwide sea-level rise at the last glacial/interglacial transition (~ 10 000 years B.P.) most probably caused the fixation of the SMT at its present position, through drastically reduced sediment delivery to the deep-sea fan. In addition, we report an internal redistribution of P occurring around the SMT, closely linked to the (de)coupling of sedimentary Fe and P, and leaving a characteristic pattern in the solid P record. By phosphate re-adsorption onto Fe (oxyhydr)oxides above, and formation of authigenic P minerals (e.g. vivianite) below the SMT, deep-sea fan deposits may potentially act as long-term sinks for P.

(Appendix 1-4) Geochemistry, desorption methods, TOC, TC, and mineral content of different settings

Sorption of volatile hydrocarbon gases (VHCs) to marine sediments is a recognized phenomenon that has been investigated in the context of petroleum exploration. However, little is known about the biogeochemistry of sorbed methane and higher VHCs in environments that are not influenced by thermogenic processes. This study evaluated two different extraction protocols for sorbed VHCs, used high pressure equipment to investigate the sorption of methane to pure clay mineral phases, and conducted a geochemical and mineralogical survey of sediment samples from different oceanographic settings and geochemical regimes that are not significantly influenced by thermogenic gas. Extraction of sediments under alkaline conditions yielded higher concentrations of sorbed methane than the established protocol for acidic extraction. Application of alkaline extraction in the environmental survey revealed the presence of substantial amounts of sorbed methane in 374 out of 411 samples (91%). Particularly high amounts, up to 2.1 mmol kg**-1 dry sediment, were recovered from methanogenic sediments. Carbon isotopic compositions of sorbed methane suggested substantial contributions from biogenic sources, both in sulfate-depleted and sulfate-reducing sediments. Carbon isotopic relationships between sorbed and dissolved methane indicate a coupling of the two pools. While our sorption experiments and extraction conditions point to an important role for clay minerals as sorbents, mineralogical analyses of marine sediments suggest that variations in mineral composition are not controlling variations in quantities of sorbed methane. We conclude that the distribution of sorbed methane in sediments is strongly influenced by in situ production.