Ce(III) and Ce(IV) (re)distribution and fractionation in a laterite profile from Madagascar: Insights from in situ XANES spectroscopy at the Ce LIII-edge

The distribution of trivalent and tetravalent cerium, Ce(III) and Ce(IV) respectively, in a lateritic profile from Madagascar, has been characterized by X-ray-absorption near-edge structure (XANES) spectroscopy at the Ce LIII-edge on the LUCIA beamline (SOLEIL synchrotron, France). XANES spectra were acquired on bulk-rock samples as well as on specific lateritic minerals or polymineral zones (in-situ measurements) of the tonalite bedrock and the three overlying weathered horizons (C-, B- and A-horizons). Geochemically, the bedrock, and the A- and C-horizons show similar rare earth element content (REE = 363–405 mg/kg). They also display the same positive Ce-anomaly (CeCN/Ce∗ = 1.12–1.45), which is therefore likely to be inherited from the bedrock. In the B-horizon, the higher REE content (REE = 2194 mg/kg) and the larger Ce-anomaly (CeCN/Ce∗ = 4.26) are consistent with an accumulation zone caused by the evaporation of groundwater during the dry season. There is a good agreement between the Ce(III)/Cetotal ratio (XCe(III)) deduced from the positive Ce-anomaly (bulk-rock geochemical data) and that derived from XANES spectroscopy on the same bulk-rock samples (BR-XCe(III)-XANES) in the bedrock, and the C- and B-horizons. In the A-horizon, XANES measurements on bulk rock and minerals revealed a higher BR-XCe(III)-XANES (up to 100%) compared to the XCe(III) deduced from geochemical data (XCe(III) = 79%). The preservation of a positive Ce-anomaly in the A-horizon suggests that the Ce mobilization and redistribution during weathering occurred with no significant Ce fractionation from other trivalent REE. Remarkably, the only investigated sample where cerianite is observed belongs to the B-horizon. Within this horizon, Ce oxidation state varies depending on the microstructural position (porosity, cracks, clay-rich groundmass). The highest Ce(IV) concentrations are measured in cerianite (and aluminophosphates) localized in pores at the vicinity of Mn-rich domains (XCe(III)-XANES = 30–51%). Therefore, Ce fractionation from other REE is attributed to a Ce oxidation and precipitation potentially assisted by oxyhydroxide scavenging. In the C-horizon, Ce(III) and Ce(IV) are mainly distributed in REE-minerals of the rhabdophane group found in pores and cracks. The similarity between the Ce(III) proportion of rhabdophane grains (XCe(III)-XANES = 74–89%) with that of the bedrock (BR-XCe(III)-XANES = 79%) suggests no significant fractionation of Ce(III) and Ce(IV) between solution and mineral during the successive stages of primary REE-mineral alteration, transport in solution and secondary precipitation in the incipient stages of weathering. Overall, our novel spectroscopic approach shows that Ce is not necessarily oxidized nor fractionated from other REE during weathering in lateritic conditions. This implies that like Ce(III), Ce(IV) can be mobilized in aqueous fluids during weathering, possibly thanks to complexation with organic molecules, and can precipitate together with Ce(III) in secondary REE-bearing minerals. The corollary is that (paleo)redox reconstructions in soils and/or sediments based on Ce-anomaly in weathered rocks or minerals must be interpreted with caution.

Late Cretaceous to Eocene calcareous nannofossil distribution near Gubbio, Italy

Using a modified sample preparation technique, we have been able to establish a detailed lower Campanian to upper Eocene nannofossil stratigraphy in the Bottaccione and Contessa Highway sections near Gubbio. Appearance and extinction levels of virtually all the commonly used calcareous nannofossil zonal markers have been recognized and can now be closely correlated with the planktonic foraminifera zonation and the magnetic reversal stratigraphy previously established in these sections. Comparisons with the nannofossil calibrations of the oceanic magnetic anomaly sequence in Deep Sea Drilling Project (DSDP) sites suggest that magmetic Subchrons C17N and C25N are missing in the Bottaccione section. The observed variability of the relative stratigraphic position of most plankton events is confirmed to less than one magnetic subchron. Absolute abundance, paleobiogeographic restriction, and differential preservation render some of the traditionally used biostratigraphic events less reliable than others.

Chemical and isotopic compositions of authigenic carbonates from the area of the Sakhalin-Deryugin gas anomaly, Sea of Okhotsk

Features of sedimentation of carbonate mineral associations in the northeastern shelf of Sakhalin and other regions of the Sea of Okhotsk are considered. Special attention is paid to correlation between carbonate neoformations and abnormal fluxes of methane. In bottom sediments with high contents of methane carbonate-sulfide associations occur, their generation has been influenced by gas (mostly methane) fields. Joint consideration of distribution of gas and geochemical fields and mineral associations in the Sea of Okhotsk allows to understand better a mechanism of mineral generation in bottom sediments, possible formation of ore accumulations, and to use them as indicators for prognosis of mineral resources.

On the fine structure of oxygen distribution in surface water layers in the area between Iceland and Faroe Islands

During the international "Overflow-Expedition'' 1973 on R.V. "Meteor" oxygen concentrations in surface layers were measured in order to determine the oxygen gradients within the first two meters and to add some informations to the mechanisms of oxygen exchange at the air-sea interface. These investigations may be interesting also with regard to longterm- observations of the oxygen distribution in the Atlantic, especially the problem of the A.O.U. (apparent oxygen utilization) determination. To measure oxygen gradients a special sampler was built which is able to take water samples each 20 cm of the first 2 meters. These data were supplemented by further samples down to 150 m, taken by conventional water samplers, from which samples were also taken to measure N2/O2-relations. By comparing these relations with theoretical relations in air-saturated water the influence of biological production and consumption on the oxygen contents in water could be estimated. A simple glass apparatus was built to extract gas from the water samples, and hereafter the N2/O2-relations were determined by mass spectrometry. Most distributions of the oxygen anomaly show a negative oxygen balance which varies largely, probably due to strong mixing processes in the Iceland-Faroe ridge area. The distribution of surface oxygen saturation values are of two different types. The values of the stations 260, 262 and 270 stem from mixed water and show homogeneous supersaturations, as can be found instantly when whitecaps appear. The values of 9 other stations are from water, sampled during calm periods which has been mixed and supersaturated before. They show a decreasing oxygen saturation towards the sea surface and often undersaturation in the upper decimeters up to 98 % and even 91 %. So at the air-sea interface even less initial oxygen saturation than 100 % can be found after supersaturation during heavy weather periods.

A total electron content space weather study of the Nighttime Weddell Sea Anomaly of 1996/97 southern summer with TOPEX/Poseidon radar altimetry

This paper reports on a total electron content space weather study of the nighttime Weddell Sea Anomaly, overlooked by previously published TOPEX/Poseidon climate studies, and of the nighttime ionosphere during the 1996/1997 southern summer. To ascertain the morphology of spatial TEC distribution over the oceans in terms of hourly, geomagnetic, longitudinal and summer-winter variations, the TOPEX TEC, magnetic, and published neutral wind velocity data are utilized. To understand the underlying physical processes, the TEC results are combined with inclination and declination data plus global magnetic field-line maps. To investigate spatial and temporal TEC variations, geographic/magnetic latitudes and local times are computed. As results show, the nighttime Weddell Sea Anomaly is a large (∼1,600(°)2; ∼22 million km2 estimated for a steady ionosphere) space weather feature. Extending between 200°E and 300°E (geographic), it is an ionization enhancement peaking at 50°S–60°S/250°E–270°E and continuing beyond 66°S. It develops where the spacing between the magnetic field lines is wide/medium, easterly declination is large-medium (20°–50°), and inclination is optimum (∼55°S). Its development and hourly variations are closely correlated with wind speed variations. There is a noticeable (∼43%) reduction in its average area during the high magnetic activity period investigated. Southern summer nighttime TECs follow closely the variations of declination and field-line configuration and therefore introduce a longitudinal division of four (Indian, western/eastern Pacific, Atlantic). Northern winter nighttime TECs measured over a limited area are rather uniform longitudinally because of the small declination variation. TOPEX maps depict the expected strong asymmetry in TEC distribution about the magnetic dip equator.

Sea-surface temperature and sea ice distribution of the Southern Ocean at the EPILOG Last Glacial Maximum

Based on the quantitative study of diatoms and radiolarians, summer sea-surface temperature (SSST) and sea ice distribution were estimated from 122 sediment core localities in the Atlantic, Indian and Pacific sectors of the Southern Ocean to reconstruct the last glacial environment at the EPILOG (19.5-16.0 ka or 23 000-19 000 cal yr. B.P.) time-slice. The statistical methods applied include the Imbrie and Kipp Method, the Modern Analog Technique and the General Additive Model. Summer SSTs reveal greater surface-water cooling than reconstructed by CLIMAP (Geol. Soc. Am. Map Chart. Ser. MC-36 (1981) 1), reaching a maximum (4-5 °C) in the present Subantarctic Zone of the Atlantic and Indian sector. The reconstruction of maximum winter sea ice (WSI) extent is in accordance with CLIMAP, showing an expansion of the WSI field by around 100% compared to the present. Although only limited information is available, the data clearly show that CLIMAP strongly overestimated the glacial summer sea ice extent. As a result of the northward expansion of Antarctic cold waters by 5-10° in latitude and a relatively small displacement of the Subtropical Front, thermal gradients were steepened during the last glacial in the northern zone of the Southern Ocean. Such reconstruction may, however, be inapposite for the Pacific sector. The few data available indicate reduced cooling in the southern Pacific and give suggestion for a non-uniform cooling of the glacial Southern Ocean.