Effects of different crystal faces on the surface charge of colloidal goethite (α-FeOOH) particles: an experimental and modeling study

The surface charge of colloidal particles is usually determined by potentiometric titration. These acid-base titrations make it possible to measure the pH of point-of-zero charge (pzc) for oxide minerals. This macroscopic property is the most important parameter used in surface complexation modeling to reproduce experimental data. The pzc values of goethite reported in the literature vary between 7.0 and 9.5. Carbonate adsorption and/or surface morphology are thought to account for this wide range.We demonstrate a procedure for the removal of the carbonate ions that initially adsorb on goethite and strongly affect the titration curves and pzc determination. We also investigated the crystal-face-specific reactivity of two morphologically different goethites. The z-profiles obtained from atomic force microscopy (AFM) images showed that the goethite with the smallest specific surface area (S = 49 m²/g, denoted G49) exhibits 70% of the (001) face, whereas this value is only 30% for the goethite with largest specific surface area (S = 95 m²/g, denoted G95). This morphologic difference results in slightly different pzc values: 9.0 for G49 goethite and 9.1 for G95 geothite. These experimental pzc values have been correlated with multisite complexation calculations using both the full-site and the 1-pK approaches. We used the full-site approach to consider all of the configurations of hydrogen bond interactions with surface site. The resulting mean charges gave estimated pzc values of 8.9 and 9.2 for the (001) and (101) faces, respectively. Considering these theoretical pzc values for individual faces and the face distributions obtained from AFM analysis, the calculated pzc values are in full agreement with the experimental pzc values. However, this morphologic difference is more expressed in surface charge values than in the pzc values. Indeed, the surface charge of G49 goethite is much higher than that of G95 goethite, and the 1-pK calculations make it possible to fit the titration data satisfactorily.     

Seston fatty acid composition and copepod RNA:DNA ratio with respect to the underwater light climate in fluvial Lac Saint-Pierre

The relationship between the underwater light availability at different wavelengths (from 351 to 700?nm) and the fatty acid (FA) composition of seston, as well as the trophic transfer of fatty acids from producers to consumers and its influence on copepod growth condition, were investigated throughout fluvial Lac Saint-Pierre (Québec, Canada). Seston and zooplankton were collected at 11 sampling sites located within distinct water masses discriminated according to their underwater spectral characteristics. Diffuse light attenuation coefficients (K_d(??)) varied among sampling sites and wavelengths (??) and were negatively correlated to seston composition in some essential fatty acids. Particularly, the relationships between K_d(??) and the seston concentration in 20:5n3 and 22:6n3 differed and were wavelength dependent, being stronger for ?? close to the absorption maxima of chlorophyll a, suggesting a potential link with photosynthetic processes. The concentrations of 16:1n7, 18:3n3 and 20:5n3 in copepods were strongly correlated to those in the seston, which points towards the trophic transfer of these fatty acids between primary producers and herbivorous consumers. Moreover, the growth condition of copepods, as expressed by their RNA:DNA ratio, was correlated to the concentrations of 16:1n7, 18:3n3 and 20:5n3 in the seston and in copepods. Our field study sheds light on the potential importance, yet to be precised, of specific wavelengths as a driver of Lac Saint-Pierre??s productivity through their influence on fatty acids composition of seston and its nutritional quality for primary consumers.     

Present weathering rates in a humid tropical watershed: Nsimi, South Cameroon

The study of biogeochemical and hydrological cycles in small experimental watersheds on silicate rocks, common for the Temperate Zone, has not yet been widely applied to the tropics, especially humid areas. This paper presents an updated database for a six-year period for the small experimental watershed of the Mengong brook in the humid tropics (Nsimi, South Cameroon). This watershed is developed on Precambrian granitoids (North Congo shield) and consists of two convexo-concave lateritic hills surrounding a large flat swamp covered by hydromorphic soils rich in upward organic matter. Mineralogical and geochemical investigations were carried out in the protolith, the saprolite, the hillside lateritic soils, and the swamp hydromorphic soils. Biomass chemical analyses were done for the representative species of the swamp vegetation. The groundwater was analysed from the parent rock/saprolite weathering front to the upper fringe in the hillside and swamp system. The chemistry of the wet atmospheric and throughfall deposits and the Mengong waters was monitored.In the Nsimi watershed the carbon transfer occurs primarily in an organic form and essentially as colloids produced by the slow biodegradation of the swamp organic matter. These organic colloids contribute significantly to the mobilization and transfer of Fe, Al, Zr, Ti, and Th in the uppermost first meter of the swamp regolith. When the organic colloid content is low (i.e., in the hillside groundwater), Th and Zr concentrations are extremely low (<3 pmol/L, ICP-MS detection limits). Strongly insoluble secondary thorianite (ThO₂) and primary zircon (ZrSiO₄) crystals control their mobilization, respectively. This finding thus justifies the potential use of both these elements as inert elements for isoelement mass balance calculations pertaining to the hillside regolith.Chloride can not be used as a conservative tracer of hydrological processes and chemical weathering in this watershed. Biogenic recycling significantly influences the low-Cl input fluxes. Sodium is a good tracer of chemical weathering in the watershed. The sodium solute flux corrected from cyclic salt input was used to assess the chemical weathering rate. Even though low (2.8 mm/kyr), the chemical weathering rate predominates over the mechanical weathering rate (1.9 mm/kyr). Compared to the Rio Icacos watershed, the most studied tropical site, the chemical weathering fluxes of silica and sodium in the Mengong are 16 and 40 times lower, respectively. This is not only related to the protective role of the regolith, thick in both cases, but also to differences in the hydrological functioning. This is to be taken into account in the calculations of the carbon cycle balance for large surfaces like that of the tropical forest ecosystems on a stable shield at the global level.     

Calc-Alkaline Magmatism at the Archean Proterozoic Transition: the Caico Complex Basement (NE Brazil)

The Paleoproterozoic metaplutonic rocks of the CaicóComplex Basement (Seridó region, NE Brazil) provide importantand crucial insights into the petrogenetic processes governingcrustal growth and may potentially be a proxy for understandingthe Archean–Proterozoic transition. These rocks consistof high-K calc-alkaline diorite to granite, with Rb–Sr,U–Pb, Pb–Pb and Sm–Nd ages of c. 2·25–2·15Ga. They are metaluminous, with high Yb_N, K₂O/Na₂O and Rb/Sr,low I_Sr ratios, and are large ion lithophile elements (LILE)enriched. Petrographic and geochemical data demonstrate thatthey belong to differentiated series that evolved by low-pressurefractionation, thus resulting in granodioritic liquids. We proposea model in which the petrogenesis of the Caicó Complexorthogneisses begins with partial melting of a metasomaticallyenriched spinel- to garnet-bearing lherzolite (with high-silicaadakite melt as the metasomatic agent), generating a basic magmathat subsequently evolved at depth through fractional crystallizationof olivine, followed by low-pressure intracrustal fractionation.A subduction zone setting is proposed for this magmatism, toaccount for both negative anomalies in high field strength elements(HFSE) and LILE enrichment. Mantle-derived juvenile magmatismwith the same age is also known in the São Franciscoand West Africa cratons, as well as in French Guyana, and thusthe Archean–Proterozoic transition marks a very importantcontinental accretion event. It also represents a transitionfrom slab-dominated (in the Archean) to wedge-dominated post-Archeanmagmatism. KEY WORDS: calc-alkaline; magmatism; NE Brazil; Paleoproterozoic; petrogenesis     

Analytic theory of Titan’s Schumann resonance: Constraints on ionospheric conductivity and buried water ocean

This study presents an approximate model for the atypical Schumann resonance in Titan’s atmosphere that accounts for the observations of electromagnetic waves and the measurements of atmospheric conductivity performed with the Huygens Atmospheric Structure and Permittivity, Wave and Altimetry (HASI–PWA) instrumentation during the descent of the Huygens Probe through Titan’s atmosphere in January 2005. After many years of thorough analyses of the collected data, several arguments enable us to claim that the Extremely Low Frequency (ELF) wave observed at around 36 Hz displays all the characteristics of the second harmonic of a Schumann resonance. On Earth, this phenomenon is well known to be triggered by lightning activity. Given the lack of evidence of any thunderstorm activity on Titan, we proposed in early works a model based on an alternative powering mechanism involving the electric current sheets induced in Titan’s ionosphere by the Saturn’s magnetospheric plasma flow. The present study is a further step in improving the initial model and corroborating our preliminary assessments. We first develop an analytic theory of the guided modes that appear to be the most suitable for sustaining Schumann resonances in Titan’s atmosphere. We then introduce the characteristics of the Huygens electric field measurements in the equations, in order to constrain the physical parameters of the resonating cavity. The latter is assumed to be made of different structures distributed between an upper boundary, presumably made of a succession of thin ionized layers of stratospheric aerosols spread up to 150 km and a lower quasi-perfect conductive surface hidden beneath the non-conductive ground. The inner reflecting boundary is proposed to be a buried water–ammonia ocean lying at a likely depth of 55–80 km below a dielectric icy crust. Such estimate is found to comply with models suggesting that the internal heat could be transferred upwards by thermal conduction of the crust, while convective processes cannot be ruled out.     

On the limits of using combined U-series/ESR method to date fossil teeth from two Early Pleistocene archaeological sites of the Orce area (Guadix-Baza basin,Spain)

The combined U-series/electron spin resonance (ESR) dating method was applied to nine teeth from two Early Pleistocene archaeological sites located in the Orce area (Guadix-Baza Basin, Southern Spain): Fuente Nueva-3 (FN-3) and Barranco León (BL). The combination of biostratigraphy and magnetostratigraphy places both sites between the Olduvai and Jaramillo subchrons (1.78–1.07 Ma).Our results highlight the difficulty of dating such old sites and point out the limits of the combined U-series/ESR dating method based on the US model. We identified several sources of uncertainties that may lead to inaccurate age estimates. Seven samples could not be dated because the dental tissues had (²³⁰Th/²³⁴U) activity ratios higher than equilibrium, indicating that uranium had probably leached from these tissues. It was however possible to calculate numerical estimates for two of the teeth, both from FN-3. One yielded a Middle Pleistocene age that seems to be strongly underestimated; the other provided an age of 1.19 ± 0.21 Ma, in agreement with data obtained from independent methods. The latter result gives encouragement that there are samples that can be used for routine dating of old sites.