Enhanced trapping of molybdenum by sulfurized marine organic matter of marine origin in Mesozoic limestones and shales

There have been many studies devoted to trace metals and their value in assessing the paleoredox conditions of ancient marine deposition. Among them, molybdenum (Mo) is frequently cited as an effective proxy for sediments and sedimentary rocks. Recently, Helz et al. (Helz, G.R., Miller, C.V., Charnock, J.M., Mosselmans, J.L.W., Pattrick, R.A.D., Garner, C.D., Vaughan, D.J., 1996. Mechanisms of molybdenum removal from the sea and its concentration in black shales: EXAFS evidences. Geochim. Cosmochim. Acta, 60, 3631-3642) and Adelson et al. (Adelson, J. M., Helz, G. R., Miller, C. V., 2001. Reconstructing the rise of recent coastal anoxia; molybdenum in Chesapeake Bay sediments. Geochim. Cosmochim. Acta, 65, 237-252.) suggested that Mo does not behave conservatively in the water column when H₂S reaches a threshold concentration. Above this concentration, a “switch” operates, and Mo is scavenged by forming bonds with metal-rich (notably iron) particles, sulfur-rich organic molecules and pyrite. In this paper, Mo-trapping by sulfur-rich organic matter (OM) in ancient marine deposits is emphasized. The following Mesozoic geological formations were selected for study because of their relatively high concentration of sulfurized OM: the Akkuyu Formation (Turkey), the Calcaires d'Orbagnoux (France) and Kimmeridge Clay (UK) and its timeequivalent in Boulonnais (France), the Kashpir oil shales (Russia), and the La Luna Formation (Venezuela). The sulfur-rich OM is identified by either measured organic-S abundance or kerogen microscope observation. Our results show that Mo is systematically more enriched relative to the other redox-sensitive/sulfide-forming elements studied (U, V, Ni, Cu, Zn, Cr), and Mo enrichment is positively correlated with the amount of sulfurized OM but not with pyrite abundance. These results illuminate the role played by sulfurized OM in geologic-scale Mo capture and retention, but they also underline the role played by reactive iron. Significant OM sulfurization is only possible when reactive iron is limited. Nevertheless, pyrite formation, though limited, could act as an initial Mo trap, prior to Mo uptake by OM that is sulfurized after the pyritization step. In future paleoenvironmental reconstructions, attention must be paid to this enhanced Mo enrichment in the presence of sulfurized organic matter. In such cases, the use of Mo could lead to overestimation of the reducing conditions of the depositional environment.     

Kinematic interpretation of folds in alpine-type peridotites

From a general understanding of the flow mechanisms in alpine-type peridotites, it is possible to describe without ambiguity the general flow regime and its directions in a massif. This result provides the means for an investigation of the origin of the folding in pyroxenitic layers independent of any preconceived theory on folding.The folds are usually isoclinal and of the flexural-flow type as demonstrated by petrofabric studies in hinges. Their axes are always parallel or subparallel to a mineral lineation which in turn is parallel or close to the orientation of the fabric elements defining the flow line. Their axial plane, which usually coincides with the foliation, is parallel to or close to the flow plane. This conclusion, also supported by paragenetic observations, shows that the folds were formed or transposed during the plastic flow responsible for the development of structures (foliation and lineation), textures and preferred mineral orientations. In the case of the Lanzo Massif and a few other Iherzolite massifs, the flow occurred during the intrusion from the mantle. The mapping in Lanzo yields evidence of a large-scale U-shaped fold with a remarkable pattern of mesoscopic folds attached to it: the tight isoclinal folds are restricted to the limbs of the largescale structure, and the open folds locally refolding former isoclinal ones to the hinge area where the angle between the folded pyroxenitic layering and the axial-plane foliation is large. Stereograms of the field structures in this hinge area clearly illustrate the geometric relations mentioned above.This folding, characterized by its axis and axial plane respectively close to the flow line and flow plane, can be explained either by rotation towards the flow line of non-cylindrical-fold axes or by direct formation in a non-plane flow when the flow line is initially contained in the layering or close to it. In this respect, the folding may bring information on the minor flow component, complementary to that given on the major flow component by considering the textures and fabrics. Finally this folding is shown to be ubiquitous in plastically deformed peridotites. It is proposed that these conclusions be extended to other domains submitted to intense non-plane flow.     

From land to sea: provenance,composition, and preservation of organic matter in a marine sediment record from the North-East Greenland shelf spanning the Younger Dryas–Holocene

The organic matter content of marine sediments is often used to infer past changes in ocean conditions. However, the organic carbon pool preserved in coastal sediments is a complex mixture derived from different sources and may not reflect in situ processes. In this study, we combine taxonomic identification of reworked palynomorphs with pyrolysis organic geochemistry and reflected-light organic petrographic microscopy to investigate the provenance, composition and preservation of organic matter in a marine sediment core retrieved from the NE Greenland shelf. Our study reveals continuous yet variable input of land-derived organic carbon to the marine environment throughout the late Younger Dryas–Holocene, with the highest input of inert carbon in the late Younger Dryas. Although the sediments contain some recent marine palynomorphs, there is no other evidence of fresh marine organic carbon. In contrast, our results indicate that these shelf sediments represent a significant sink of recycled organic carbon. The results of pyrolysis geochemistry revealed that ~90% of the total organic carbon in the sediments is inert. The organic petrography analyses revealed that >70–84% of the organic carbon in the sediment core is terrigenous. Reworked dinoflagellate cysts showed a continuous provenance of Cretaceous land-derived material, most likely from the nearby Clavering Island. Our study points to the importance of constraining the organic matter origin, composition and preservation in marine sediments to achieve more accurate palaeoenvironmental reconstructions based on organic proxies.     

Fertilization and pH effects on processes and mechanisms controlling dissolved inorganic phosphorus in soils

We used of a set of mechanistic adsorption models (1-pK TPM, ion exchange and Nica-Donnan) within the framework of the component additive (CA) approach in an attempt to determine the effect of repeated massive application of inorganic P fertilizer on the processes and mechanisms controlling the concentration of dissolved inorganic phosphorus (DIP) in soils. We studied the surface layer of a Luvisol with markedly different total concentrations of inorganic P as the result of different P fertilizer history (i.e. massive or no application for 40 years). Soil pH was made to vary from acid to alkaline. Soil solutions were extracted with water and CaCl₂ (0.01 M). The occurrence of montmorillonite led us to determine the binding properties of P and Ca ions for this clay mineral.Satisfactory results were obtained using generic values for model parameters and soil-specific ones, which were either determined directly by measurements or estimated from the literature. We showed that adsorption largely controlled the variations of DIP concentration and that, because of kinetic constrains, only little Ca-phosphates may be precipitated under alkaline conditions, particularly in the P fertilized treatment. The mineral-P pool initially present in both P treatments did not dissolve significantly during the course of the experiments. The adsorption of Ca ions onto soil minerals also promoted adsorption of P ions through electrostatic interactions. The intensity of the mechanism was high under neutral to alkaline conditions. Changes in DIP concentration as a function of these environmental variables can be related to changes in the contribution of the various soil minerals to P adsorption. The extra P adsorbed in the fertilized treatment compared with the control treatment was mainly adsorbed onto illite. This clay mineral was the major P-fixing constituent from neutral to alkaline pH conditions, because the repulsion interactions between deprotonated hydroxyl surface sites and P ions were sufficiently counterbalanced by Ca ions. The drastic increase of DIP observed at acid pH was due to the effect of the lower concentration of surface sites of Fe oxides and kaolinite.In addition to confirming the validity of our approach to model DIP concentrations in soils, the present investigation showed that adsorption was the predominant geochemical process even in the P fertilized soil, and that Ca ions can have an important promoting effect on P adsorption. However the influence of the dissolution of the mineral-P pool under field conditions remained questionable.     

Mineral paragenesis of the Kalahari managanese field, South Africa

The mineralogy of the managanese ores of the giant Paleoproterozoic Kalahari manganese deposit of the Transvaal Supergroup has been subject of many studies and up to now 135 different ore and gangue minerals have been described, of which eight represent new mineral species. Through correlation of different mineral assemblages with specific geological events and by determining relative ages of minerals in outcrop, hand specimen and under the microscope an attempt is made in this publication to construct a paragenetic sequence for this complex mineral assemblage. Sedimentation and early diagenesis of the Hotazel Formation, composed of interbedded iron formation and braunite lutite, was followed by low-grade metamorphism and associated stratabound metasomatism. Braunite lutite of sedimentary origin, comprising 97% of the total ore reserve, is composed of braunite, hematite and kutnahorite, and abundant early diagenetic kutnahorite and manganoan calcite forming laminae and ovoids. Fluid flow during late diagenesis or lower greenschist facies metamorphism led to stratabound metasomatic oxidation of Mn-bearing carbonates to hausmannite and Mn-poor calcite. Three structurally controlled hydrothermal alteration events succeed metamorphism. These events are referred to as Wessels, Mamatwan and Smartt events. The Wessels alteration event is the oldest of the three events and it is of great economic importance because virtually all of the high-grade ore (> 42% Mn), 3% of the total ore reserve, formed during this event through alteration of carbonate-rich low-grade Mamatwan-type ore (braunite lutite) to high-grade, carbonate-poor Wessels-type manganese ore. This Wessels hydrothermal alteration event took place in the northwestern part of the Kalahari deposit, associated with a system of major north-south- and minor east-west-striking normal faults. The Mamatwan alteration event is observed throughout the Kalahari manganese deposit but alteration is very localized. Reduction halos and discolouration of braunite lutite around fracture or joint-hosted sulphide-carbonate mineralization are typical of the Mamatwan alteration event. In contrast, the Smartt alteration event is characterized by oxidation of braunite lutite and the formation of todorokite and manganomelane. Syn- and Post-Kalahari supergene alteration has taken place below the suboutcrop of the Hotazel Formation against the calcretized sediments of the Cenozoic Kalahari Formation. Cryptomelane and pyrolusite are the predominant products of surficial weathering.     

Melting of Fe–Ni–Si and Fe–Ni–S alloys at megabar pressures: implications for the core–mantle boundary temperature

High pressure melting behavior of three Fe-alloys containing 5 wt% Ni and (1) 10 wt% Si, (2) 15 wt% Si or (3) 12 wt% S was investigated up to megabar pressures by in situ X-ray diffraction and laser-heated diamond anvil cell techniques. We observe a decrease in melting temperature with increasing Si content over the entire investigated pressure range. This trend is used to discuss the melting curve of pure Fe. Moreover, our measurements of eutectic melting in the Fe–Fe₃S system show a change in slope around 50 GPa concomitant with the fcc–hcp phase transition in pure solid iron. Extrapolations of our melting curve up to the core–mantle boundary pressure yield values of 3,600–3,750 K for the freezing temperature of plausible outer core compositions.     

Consistency and fidelity of Indonesian-throughflow total volume transport estimated by 14 ocean data assimilation products

Monthly averaged total volume transport of the Indonesian throughflow (ITF) estimated by 14 global ocean data assimilation (ODA) products that are decade to multi-decade long are compared among themselves and with observations from the INSTANT Program (2004–2006). The main goals of the comparisons are to examine the consistency and evaluate the skill of different ODA products in simulating ITF transport. The ensemble averaged, time-mean value of ODA estimates is 13.6 Sv (1 Sv = 10⁶ m³/s) for the common 1993–2001 period and 13.9 Sv for the 2004–2006 INSTANT Program period. These values are close to the 15-Sv estimate derived from INSTANT observations. All but one ODA time-mean estimate fall within the range of uncertainty of the INSTANT estimate. In terms of temporal variability, the scatter among different ODA estimates averaged over time is 1.7 Sv, which is substantially smaller than the magnitude of the temporal variability simulated by the ODA systems. Therefore, the overall “signal-to-noise” ratio for the ensemble estimates is larger than one. The best consistency among the products occurs on seasonal-to-interannual time scales, with generally stronger (weaker) ITF during boreal summer (winter) and during La Nina (El Nino) events. The scatter among different products for seasonal-to-interannual time scales is approximately 1 Sv. Despite the good consistency, systematic difference is found between most ODA products and the INSTANT observations. All but the highest-resolution (18 km) ODA product show a dominant annual cycle while the INSTANT estimate and the 18-km product exhibit a strong semi-annual signal. The coarse resolution is an important factor that limits the level of agreement between ODA and INSTANT estimates. Decadal signals with periods of 10–15 years are seen. The most conspicuous and consistent decadal change is a relatively sharp increase in ITF transport during 1993–2000 associated with the strengthening tropical Pacific trade wind. Most products do not show a weakening ITF after the mid-1970s’ associated with the weakened Pacific trade wind. The scatter of ODA estimates is smaller after than before 1980, reflecting the impact of the enhanced observations after the 1980s. To assess the representativeness of using the average over a three-year period (e.g., the span of the INSTANT Program) to describe longer-term mean, we investigate the temporal variations of the three-year low-pass ODA estimates. The average variation is about 3.6 Sv, which is largely due to the increase of ITF transport from 1993 to 2000. However, the three-year average during the 2004–2006 INSTANT Program period is within 0.5 Sv of the long-term mean for the past few decades.     

L'inclinométrie,un nouvel outil pour le suivi temporel des aquifères ?

This study explores the sensitivity of tilt measurements to hydrogeologic phenomena in order to use them to characterise aquifers and explain the signals observed on the instruments. The challenge is to separate the hydrogeological contribution from other phenomena that affect this type of measurements. First, we applied the theory propounded by Farell (1972) and Pagiatakis (1990) to simple hydrogeological cases. Then a simulation of the tiltmeter signal obtained in the Seine valley reveals that the order of magnitude is significant: the signal of a load with hydrologic origin therefore represents a significant part of any tiltmeter signal. Moreover, it can be interpreted in hydrogeological terms: it depends directly on the load gradient through a convolution formalism. Consequently, it is possible to imagine a use of the tiltmeter in hydrogeology to characterise, to a certain extent, mass transfer of water in the ground. To cite this article: T. Rerolle et al., C. R. Geoscience 338 (2006).