Thermodynamic properties of chlorite and berthierine derived from calorimetric measurements

In the context of the deep waste disposal, we have investigated the respective stabilities of two iron-bearing clay minerals: berthierine ISGS from Illinois [USA; (Al_0.975FeIII_0.182FeII_1.422Mg_0.157Li_0.035Mn_0.002)(Si_1.332Al_0.668)O₅(OH)₄] and chlorite CCa-2 from Flagstaff Hill, California [USA; (Si_2.633Al_1.367)(Al_1.116FeIII_0.215Mg_2.952FeII_1.712Mn_0.012Ca_0.011)O₁₀(OH)₈]. For berthierine, the complete thermodynamic dataset was determined at 1 bar and from 2 to 310 K, using calorimetric methods. The standard enthalpies of formation were obtained by solution-reaction calorimetry at 298.15 K, and the heat capacities were measured by heat-pulse calorimetry. For chlorite, the standard enthalpy of formation is measured by solution-reaction calorimetry at 298.15 K. This is completing the entropy and heat capacity obtained previously by Gailhanou et al. (Geochim Cosmochim Acta 73:4738–4749, 2009) between 2 and 520 K, by using low-temperature adiabatic calorimetry and differential scanning calorimetry. For both minerals, the standard entropies and the Gibbs free energies of formation at 298.15 K were then calculated. An assessment of the measured properties could be carried out with respect to literature data. Eventually, the thermodynamic dataset allowed realizing theoretical calculations concerning the berthierine to chlorite transition. The latter showed that, from a thermodynamic viewpoint, the main factor controlling this transition is probably the composition of the berthierine and chlorite minerals and the nature of the secondary minerals rather than temperature.     

Surface Expressions of Rayleigh-Taylor Instability in Continental Interiors

Two-dimensional thermal-mechanical numerical models show that Rayleigh-Taylor-type （RT） gravitational removal of high-density lithosphere may produce significant surface deformation （vertical deflection 〉1000 m） in the interior of a continental plate.A reasonable range of crustal strengths and thicknesses,representing a variation from a stable continental interior to a hot orogen with a thick crust,is examined to study crustal deformation and the surface deflection in response to an RT instability.In general,three types of surface deflection are observed during the RT drip event：（1） subsidence and negative topography; （2） uplift and positive topography; （3） subsidence followed by uplift and inverted topography.One key factor that determines the surface expression is the crustal thickness.Models with a thin crust mainly show subsidence and develop a basin.In the thick crust models,surface expressions are more variable,depending on the crustal strength and depth of highdensity anomaly.With weak crust and a deep high-density anomaly,the RT drip is decoupled from the overlying crust,and the surface exhibits uplift or little deflection,as the RT drip induces contraction and thickening of the overlying crust.In contrast,with a strong crust and shallow anomaly,the surface is more strongly coupled with the drip and undergoes subsidence,followed by uplift.     

A probabilistic investigation of infiltration in the vadose zone: proposal for a new formula of infiltration rate

The infiltration rate in the unsaturated zone is analysed from a probabilistic point of view. It is shown that the empirical formulas of Horton and Kostiakov, without apparent physical basis, are explained in a probabilistic approach. Horton's formula reflects a Markovian process contrary to Kostiakov's formula. This approach made it possible to explain why Kostiakov's formula is more powerful than that of Horton. A new equation of infiltration is proposed. The three formulas were compared, for four types of soil, with the model of van Genuchten based on the Richards equation. Copyright © 2006 John Wiley & Sons, Ltd.     

Palaeoenvironmental response to the ∼74 ka Toba ash-fall in the Jurreru and Middle Son valleys in southern and north-central India

Distal deposits of rhyolitic volcanic ash from the ∼74 ka “supervolcanic” eruption of Toba, in northern Sumatra, are preserved in numerous river valleys across peninsular India. The Toba eruption is hypothesized to have resulted in climate change and the devastation of ecosystems and hominin populations. This study reports the results of the analysis of sediments and stratigraphical sequences from sites in the Jurreru and Middle Son valleys in southern and north-central India. The aim of the study is to determine the extent of palaeoenvironmental change in both valleys as a result of the ash-fall. Inferences based on evidence from the Jurreru valley are more detailed, where pre- and post-Toba palaeoenvironmental changes are divided into seven phases. The results indicate that ash-fall deposits in both valleys underwent several phases of reworking that possibly lasted for several years, indicating that ash was mobile in the landscape for a considerable period of time prior to burial. This could have enhanced and lengthened the detrimental effects of the ash on vegetation and water sources, as well as animal and hominin populations.     

Whole-basin,mass-balance approach for identifying critical phosphorus-loading thresholds in shallow lakes

Lake Lochloosa, Florida (USA) recently underwent a shift from macrophyte to phytoplankton dominance, offering us the opportunity to use a whole-basin, mass-balance approach to investigate the influence of phosphorus loading on ecosystem change in a shallow, sub-tropical lake. We analyzed total phosphorus (TP) sedimentation in the basin to improve our understanding of the forcing factor responsible for the recent shift to phytoplankton dominance. We measured ²¹⁰Pb activity, organic matter (OM), organic carbon (OC) and TP in short sediment cores from 20 locations to develop a comprehensive, whole-basin estimate of recent mass sedimentation rates (MSR) for bulk sediment, OM, OC and TP. The whole-basin sedimentation models provided insights into historic lake processes that were not evident from the limited, historic water quality data. We used Akaike’s Information Criteria to differentiate statistically between constant MSR and exponentially increasing MSR. An eightfold, exponential increase in TP accumulation over the past century provided evidence for the critical role of increased P loading as a forcing factor in the recent shift to phytoplankton dominance. Model results show increased TP retention and decreased TP residence time were in-lake responses to increased TP loading and the shift from macrophyte to phytoplankton dominance in Lake Lochloosa. Comparison of TP loading with TP retention and historic, diatom-inferred limnetic TP concentrations identified the TP loading threshold that was exceeded to trigger the shift to phytoplankton dominance.     

Evaluation of LPATS data using VHF interferometric observations of lightning flashes during the Eulinox experiment

During the Eulinox (European Lightning Nitrogen Oxides Project) campaign, two lightning sensors were available: a Lightning Position and Tracking System (LPATS), and the ONERA VHF interferometric (ITF) mapper. We looked for the typical VHF signature of positive and negative cloud-to-ground flashes in ITF records in order to separate intra-cloud (IC) flashes from cloud-to-ground (CG) flashes during five periods from 2 days. Then we used this set of data to check the efficiency of the South Germany LPATS. We concluded that this LPATS detected nearly all the negative CG flashes, but one-fourth of LPATS negative strokes are in fact IC flashes. The ratio of misinterpretation is much smaller (15%) for multi-stroke negative CG flashes. The LPATS recorded 62% of the positive strokes, but only 43% with the right polarity, and only 25% of LPATS positive strokes actually belonged to a positive CG flash. This reliability ratio is 100% if we consider only high-intensity LPATS strokes.     

Preliminary study on the preservation of giant clam (Tridacnidae) shells from the Balobok Rockshelter archaeological site,south Philippines

Tridacnidae shells, a valuable archive of past environments, are common in the Balobok Rockshelter archaeological site on Sanga‐Sanga Island in the south Philippines. This site was occupied during the mid‐Holocene (ca. 5000–8800 ¹⁴C yr B.P.), a period of Neolithic cultural expansion in the Philippines. This paper focuses on the preservation of two shell specimens, Hippopus hippopus and Tridacna maxima, unearthed from two mid‐Holocene layers within the rockshelter. The shells' mineralogy and microstructure (prismatic and crossed‐lamellar) were studied using micro‐Fourier transform infrared spectroscopy and scanning electron microscopy to determine if the samples were suitable as paleoenvironmental records. Both shells are still aragonitic but aragonite crystals of both microstructure types are partly dissolved. This dissolution, characteristic of meteoric water alteration, precludes their utility in paleoenvironmental geochemical studies. Nevertheless, these shells are abundant in archaeological sites in the region and may be better preserved in other depositional contexts; more studies on Philippine Tridacnidae shell diagenesis are needed. © 2011 Wiley Periodicals, Inc.