Potentiometric titrations of Bacillus subtilis cells to low pH and a comparison of modeling approaches

To provide constraints on the speciation of bacterial surface functional groups, we have conducted potentiometric titrations using the gram-positive aerobic species Bacillus subtilis, covering the pH range 2.1 to 9.8. Titration experiments were conducted using an auto-titrator assembly, with the bacteria suspended in fixed ionic strength (0.01 to 0.3 M) NaClO₄ solutions. We observed significant adsorption of protons over the entire pH range of this study, including to the lowest pH values examined, indicating that proton saturation of the cell wall did not occur under any of the conditions of the experiments. Ionic strength, over the range studied here, did not have a significant effect on the observed buffering behavior relative to experimental uncertainty. Electrophoretic mobility measurements indicate that the cell wall is negatively charged, even under the lowest pH conditions studied. These experimental results necessitate a definition of the zero proton condition such that the total proton concentration at the pH of suspension is offset to account for the negative bacterial surface charge that tends towards neutrality at pH <2.The buffering intensity of the bacterial suspensions reveals a wide spread of apparent pKa values. This spread was modeled using three significantly different approaches: a Non-Electrostatic Model, a Constant Capacitance Model, and a Langmuir-Freundlich Model. The approaches differ in the manner in which they treat the surface electric field effects, and in whether they treat the proton-active sites as discrete functional groups or as continuous distributions of related sites. Each type of model tested, however, provides an excellent fit to the experimental data, indicating that titration data alone are insufficient for characterizing the molecular-scale reactions that occur on the bacterial surface. Spectroscopic data on the molecular-scale properties of the bacterial surface are required to differentiate between the underlying mechanisms of proton adsorption inherent in these models. The applicability and underlying conceptual foundation of each model is discussed in the context of our current knowledge of the structure of bacterial cell walls.     

Groundwater metering: revisiting a ubiquitous ‘best practice’

Hydrogeology Journal - It is often taken for granted that metering is an unarguable ‘best practice’ when it comes to the quantitative management of groundwater resources. This paper...     

An X-ray absorption fine structure and nuclear magnetic resonance spectroscopy study of gallium-silica complexes in aqueous solution

The influence of aqueous silica on gallium(III) hydrolysis in dilute (2 × 10⁻⁴ ≤ m_Ga ≤ 5 × 10⁻³) and moderately concentrated (0.02 ≤ m_Ga ≤ 0.3) aqueous solutions was studied at ambient temperature, using high resolution X-ray absorption fine structure (XAFS) and nuclear magnetic resonance (NMR) spectroscopies, respectively. Results show that, in Si-free acidic solutions (pH < 3), Ga is hexa-coordinated with oxygens of H₂O molecules and/or OH groups in the first coordination sphere of the metal. With increasing pH, these hydroxyl groups are progressively replaced by bridging oxygens (-O-), and polymerized Ga-hydroxide complexes form via Ga-O-Ga chemical bonds. In the 2.5-3.5 pH range, both XAFS and NMR spectra are consistent with the dominant presence of the Ga₁₃ Keggin polycation, which has the same local structure as A1₁₃. Under basic pH (pH > 8), Ga exhibits a tetrahedral coordination, corresponding to Ga(OH)₄⁻ species, in agreement with previous NMR and potentiometric studies. Major changes in Ga hydrolysis have been detected in the presence of aqueous silica. Ga is tetra-coordinated, both in basic and acid (i.e., at pH > 2.7) Si-bearing solutions (0.01 ≤ m_Si ≤ 0.2), and forms stable gallium-silicate complexes. In these species, Ga binds via bridging oxygen to 2 ± 1 silicons, with an average Ga-Si distance of 3.16 ± 0.05 Å, and to 2 ± 1 silicons, with an average Ga-Si distance of 3.39 ± 0.03 Å. These two sets of Ga-Si distances imply the formation of two types of Ga-silicate aqueous complex, cyclic Ga-Si_2-3 species (formed by the substitution of Si in its tri-, tetra- or hexa-cyclic polymers by Ga atoms), and chainlike GaSi_2-4 species (similar to those found for A1), respectively. The increase in the number of Si neighbors (a measure of the complex concentration and stability), in alkaline media, with increasing SiO₂(aq) content and decreasing pH is similar to that for A1-Si complexes found in neutral to basic solutions. At very acid pH and moderate silica concentrations, the presence of another type of Ga-Si complex, in which Ga remains hexa-coordinated and binds to the silicon tetrahedra via the GaO₆ octahedron corners, has also been detected. These species are similar to those found for Al³⁺ in acid solutions. Thus, as for aluminum, silicic acid greatly hampers Ga hydrolysis and enhances Ga mobility in natural waters via the formation of gallium-silicate complexes.     

Late Quaternary vegetation and climate dynamics in central-eastern Brazil: insights from a ~35k cal a bp peat record in the Cerrado biome

The late Quaternary evolution of central-eastern Brazil has been under-researched. Questions remain as to the origin of the Cerrado, a highly endangered biome, and other types of vegetation, such as the Capões – small vegetation islands of semi-deciduous and mountain forests. We investigated the factors that influenced the expansion and contraction of the Cerrado and Capões during the late Quaternary (last ~35 ka), using a multi-proxy approach: stable isotopes (δ¹³C, δ¹⁵N), geochemistry, pollen and multivariate statistics derived from a peat core (Pinheiro mire, Serra do Espinhaço Meridional). Five major shifts in precipitation, temperature, vegetation and landscape stability occurred at different timescales. Our study revealed that changes in the South Atlantic Convergence Zone (SACZ) seem to have been coeval with these shifts: from the Late Glacial Maximum to mid-Holocene the SACZ remained near (~29.6 to ~16.5k cal a bp ) and over (~16.5 to ~6.1 k cal a bp ) the study area, providing humidity to the region. This challenges previous research which suggested that climate was drier for this time period. At present, the Capões are likely to be a remnant of a more humid climate; meanwhile, the Cerrado biome seems to have stablished in the late Holocene, after ~3.1 k cal a bp .     

Landslide susceptibility mapping of the Sera River Basin using logistic regression model

Of the natural hazards in Turkey, landslides are the second most devastating in terms of socio-economic losses, with the majority of landslides occurring in the Eastern Black Sea Region. The aim of this study is to use a statistical approach to carry out a landslide susceptibility assessment in one area at great risk from landslides: the Sera River Basin located in the Eastern Black Sea Region. This paper applies a multivariate statistical approach in the form of a logistics regression model to explore the probability distribution of future landslides in the region. The model attempts to find the best fitting function to describe the relationship between the dependent variable, here the presence or absence of landslides in a region and a set of independent parameters contributing to the occurrence of landslides. The dependent variable (0 for the absence of landslides and 1 for the presence of landslides) was generated using landslide data retrieved from an existing database and expert opinion. The database has information on a few landslides in the region, but is not extensive or complete, and thus unlike those normally used for research. Slope, angle, relief, the natural drainage network (including distance to rivers and the watershed index) and lithology were used as independent parameters in this study. The effect of each parameter was assessed using the corresponding coefficient in the logistic regression function. The results showed that the natural drainage network plays a significant role in determining landslide occurrence and distribution. Landslide susceptibility was evaluated using a predicted map of probability. Zones with high and medium susceptibility to landslides make up 38.8 % of the study area and are located mostly south of the Sera River Basin and along streams.     

Field evidences of secondary surface ruptures occurred during the 20 February 1956 Eskişehir earthquake in the NW Anatolia

Surface rupture and source fault of the 20 February 1956 Eskişehir earthquake have been a matter of debate that potentially contributes towards the understanding of the active deformation and seismic risk in the highly populated NW Anatolia. Field observations on the two fault segments (namely Kavacık and Uludere faults) in the north of the Eskişehir graben revealed evidences of co-seismic surface rupture and mass movements during the Eskişehir earthquake. Surface rupture was observed as a 2.5m wide, a 100m long and ca. 20 cm deep asymmetric depression in the Gümüşlü valley, 2 km east of the Uludere village. A trench dug on this depression confirms a prominent high-angle south dipping fault (dominantly left lateral strike slip) and two faint north-dipping antithetics as clear noticeable shear zones in organic-rich thick soil. Mass failures are particularly observed in spring depressions filled with loose torrent and carbonaceous material in front of the fault scarp. Some rock slides of several tens of meters in size that obviously require significantly high ground shaking were also developed on steep fault scarps. The orientation of the principal stress tensor as deduced from the surface rupture of the Eskişehir earthquake displays clear inconsistency with the geometry of prominent faults in the area. We concluded that this disagreement may be explained by a curved surface rupture. The western and eastern tips of this rupture are EW trending and the probable NW-running part in the middle would correspond to the bounding zone between two right-stepping faults.     

Cooling history of nested plutons from the Variscan Tichka plutonic complex (Morocco)

International Journal of Earth Sciences - Four imbricated mafic to felsic plutons of Variscan age from Morocco have been investigated for their cooling history and geochemical interactions with...     

Ion transport in porous media: derivation of the macroscopic equations using upscaling and properties of the effective coefficients

In this work, we undertake a numerical study of the effective coefficients arising in the upscaling of a system of partial differential equations describing transport of a dilute N-component electrolyte in a Newtonian solvent through a rigid porous medium. The motion is governed by a small static electric field and a small hydrodynamic force, around a nonlinear Poisson–Boltzmann equilibrium with given surface charges of arbitrary size. This approach allows us to calculate the linear response regime in a way initially proposed by O’Brien. The O’Brien linearization requires a fast and accurate solution of the underlying Poisson–Boltzmann equation. We present an analysis of it, with the discussion of the boundary layer appearing as the Debye–Hückel parameter becomes large. Next, we briefly discuss the corresponding two-scale asymptotic expansion and reduce the obtained two-scale equations to a coarse scale model. Our previous rigorous study proves that the homogenized coefficients satisfy Onsager properties, namely they are symmetric positive definite tensors. We illustrate with numerical simulations several characteristic situations and discuss the behavior of the effective coefficients when the Debye–Hückel parameter is large. Simulated qualitative behavior differs significantly from the situation when the surface potential is given (instead of the surface charges). In particular, we observe the Donnan effect (exclusion of co-ions for small pores).     

Relations entre les données isotopiques océaniques et l'histoire des grandes faunes européennes plio-pleistocenes

This study is the first test of correlation between the results obtained on the large Plio-Pleistocene European faunas and the main climatic stages (cold as well as temperate) demonstrated in marine isotopic records. In particular, there are cold stages which often explain the disappearance of some species, as well as climatic events that promote the substitution of some species by other groups. A rather evident parallelism appears between the European succession of large faunal associations and paleoclimatic stages revealed in oceanic areas, but some discordance occurs in the later periods. Faced with the great diversification of the Quaternary faunas, probably due to the multiplicity of climatic environments, and with global information from oceanic records, only local biostratigraphic studies will allow precise reconstruction of the different biotopes.     

Stable isotope study of antimony deposits in the Muratdagi region,western Turkey

The Muratdagi region is rich in antimony deposits having the following common characteristics: post Miocene age, location on the down-thrown blocks next to normal faults, in the vicinity of active or fossil thermal springs, and in contact with carbonate rocks. The isotopic composition of — 7. SMOW of the mineralizing fluid calculated from the measured ° ¹⁸O of quartz and the fluid inclusion microthermometry, is indicative of meteoric water origin. The ° ¹³C of the inclusion CO₂ of — 19.1 to — 25.4 PDB is indicative of interaction with organic material-graphite. The ° ³⁴S of stibnite — 3.6 to — 0.7 is, in view of the mineral assemblage, indicative of magmatic origin of the sulphur. A tightly confined set of structural, lithological, hydrological and geochemical features define a sequence of geochemical processes; formation of acid and reducing fluid, leaching and transport of antimony complexes and precipitation of stibnite within defined lithological units. The set of processes seems to have taken place within a space of 5000 m lateral and 1000 m vertical extension.