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).     

Early Cretaceous (late Berriasian to early Aptian) palaeoceanographic change along the northwestern Tethyan margin (Vocontian Trough,southeastern France): δ13C, δ18O and Sr-isotope belemnite and whole-rock records

Stable carbon, oxygen, and strontium isotope records were obtained from uppermost Hauterivian to lowermost Aptian belemnite rostra, which were collected in well-dated sections from the Vocontian Trough (southeastern France). This data set complements previously published belemnite-isotope records from the uppermost Berriasian-Hauterivian interval from the same basin. The belemnite carbon and oxygen isotope record is compared to the carbonate bulk-rock isotope record from the same sections, and from additional Italian sections. With regards to their long-term trends, both belemnite and whole-rock δ¹⁸O records are well correlated, except for the uppermost Hauterivian-lower Barremian interval, within which they deviate. This discrepancy is interpreted to be linked to the latest Hauterivian Faraoni oceanic anoxic event and its early Barremian aftermath. The Faraoni level is characterized by enhanced sea-water stratification, probably induced by the onset of a warmer and more humid climate along the northern Tethyan margin. The early Barremian was characterized by stronger vertical sea-water mixing reflected by a decrease in density contrast between sea-surface and deeper waters. The belemnite oxygen isotope record shows a more stable evolution with smaller fluctuations than its bulk-rock counterpart, which indicates that deeper water masses were not as much subjected to density fluctuations as sea-surface water. The comparison of belemnite and bulk-rock carbon isotope records allows observing the impact of regional influence exerted by platform carbonate ooze shedding on the carbon cycle. Discrepancies in the two records are observed during time of photozoan carbonate platform growth. The strontium isotopic record shows a gradual increase from the uppermost Berriasian to the uppermost lower Barremian followed by a rapid decrease until the uppermost Barremian and a renewed small increase within the lowermost Aptian. The major inflection point in the uppermost lower Barremian appears to predate the onset in the formation of the Ontong-Java volcanic plateau.