Semi-empirical proton binding constants for natural organic matter

Average proton binding constants (K_H,i) for structure models of humic (HA) and fulvic (FA) acids were estimated semi-empirically by breaking down the macromolecules into reactive structural units (RSUs), and calculating K_H,i values of the RSUs using linear free energy relationships (LFER) of Hammett. Predicted log K_H,COOH and log K_H,Ph-OH are 3.73 ± 0.13 and 9.83 ± 0.23 for HA, and 3.80 ± 0.20 and 9.87 ± 0.31 for FA. The predicted constants for phenolic-type sites (Ph-OH) are generally higher than those derived from potentiometric titrations, but the difference may not be significant in view of the considerable uncertainty of the acidity constants determined from acid-base measurements at high pH. The predicted constants for carboxylic-type sites agree well with titration data analyzed with Model VI (4.10 ± 0.16 for HA, 3.20 ± 0.13 for FA; Tipping, 1998), the Impermeable Sphere model (3.50-4.50 for HA; Avena et al., 1999), and the Stockholm Humic Model (4.10 ± 0.20 for HA, 3.50 ± 0.40 for FA; Gustafsson, 2001), but differ by about one log unit from those obtained by Milne et al. (2001) with the NICA-Donnan model (3.09 ± 0.51 for HA, 2.65 ± 0.43 for FA), and used to derive recommended generic values. To clarify this ambiguity, 10 high-quality titration data from Milne et al. (2001) were re-analyzed with the new predicted equilibrium constants. The data are described equally well with the previous and new sets of values (R² ? 0.98), not necessarily because the NICA-Donnan model is overparametrized, but because titration lacks the sensitivity needed to quantify the full binding properties of humic substances. Correlations between NICA-Donnan parameters are discussed, but general progress is impeded by the unknown number of independent parameters that can be varied during regression of a model fit to titration data. The high consistency between predicted and experimental K_H,COOH values, excluding those of Milne et al. (2001), gives faith in the proposed semi-empirical structural approach, and its usefulness to assess the plausibility of proton stability constants derived from simulations of titration data.     

Inhomogeneous viscous fluids in FRW universe and finite-future time singularities

We consider inhomogeneous viscous fluids in flat Friedmann-Robertson-Walker universe. We analyze different kinds of such fluids and investigate the possibility to reproduce the current cosmic acceleration providing a different future evolution with respect to the Cosmological Constant case. In particular, we study the presence of finite-future time singularities. We also discuss a general class of “integrable” viscous fluid models whose bulk viscosities obey to a common differential equation.     

Speciation and solubility of heavy metals in contaminated soil using X-ray microfluorescence, EXAFS spectroscopy, chemical extraction, and thermodynamic modeling

Synchrotron-based X-ray radiation microfluorescence (μ-SXRF) and micro-focused and powder extended X-ray absorption fine structure (EXAFS) spectroscopy measurements, combined with desorption experiments and thermodynamic calculations, were used to evaluate the solubility of metal contaminants (Zn, Cu, Pb) and determine the nature and fractional amount of Zn species in a near-neutral pH (6.5-7.0) truck-farming soil contaminated by sewage irrigation for one hundred years. Zn is the most abundant metal contaminant in the soil (1103 mg/kg), followed by Pb (535 mg/kg) and Cu (290 mg/kg). The extractability of Zn, Pb, and Cu with citrate, S,S-ethylenediaminedisuccinic acid (EDDS), and ethylenediaminetetraacetic acid (EDTA) was measured as a function of time (24 h, 72 h, 144 h), and also as a function of the number of applications of the chelant (5 applications each with 24 h of contact time). Fifty-three percent of the Zn was extracted after 144 h with citrate, 51% with EDDS and 46% with EDTA, compared to 69, 87, and 61% for Cu, and 24, 40, and 34% for Pb. Renewing the extracting solution removed more of the metals. Seventy-nine, 65, and 57% of the Zn was removed after five cycles with citrate, EDDS and EDTA, respectively, compared to 88, 100, and 72% for Cu, and 91, 65, and 47% for Pb. Application to the untreated soil of μ-SXRF, laterally resolved μ-EXAFS combined with principal component analysis, and bulk averaging powder EXAFS with linear least-squares combination fit of the data, identified five Zn species: Zn-sorbed ferrihydrite, Zn phosphate, Zn-containing trioctahedral phyllosilicate (modeled by the Zn kerolite, Si₄(Mg_1.65Zn_1.35)O₁₀(OH)₂ · nH₂O), willemite (Zn₂SiO₄), and gahnite (ZnAl₂O₄), in proportions of ∼30, 28, 24, 11, and less than 10%, respectively (precision: 10% of total Zn). In contrast to Cu and Pb, the same fractional amount of Zn was extracted after 24 h contact time with the three chelants (40-43% of the initial content), suggesting that one of the three predominant Zn species was highly soluble under the extraction conditions. Comparison of EXAFS data before and after chemical treatment revealed that the Zn phosphate component was entirely and selectively dissolved in the first 24 h of contact time. Preferential dissolution of the Zn phosphate component is supported by thermodynamic calculations. Despite the long-term contamination of this soil, about 79% of Zn, 91% of Pb, and 100% of Cu can be solubilized in the laboratory on a time scale of a few days by chemical complexants. According to metal speciation results and thermodynamic calculations, the lower extraction level measured for Zn is due to the Zn phyllosilicate component, which is less soluble than Zn phosphate and Zn ferrihydrite.     

Dynamical constraints on some orbital and physical properties of the WD0137-349A/B binary system

In this paper I deal with the WD0137-349 binary system consisting of a white dwarf (WD) and a brown dwarf (BD) in a close circular orbit of about 116 min. I, first, constrain the admissible range of values for the inclination i by noting that, from looking for deviations from the third Kepler law, the quadrupole mass moment Q would assume unlikely large values, incompatible with zero at more than 1-sigma level for i≲35 deg and i≳43 deg. Then, by conservatively assuming that the most likely values for i are those that prevent such an anomalous behavior of Q, i.e. those for which the third Kepler law is an adequate modeling of the orbital period, I obtain i=39±2 deg. Such a result is incompatible with the value i=35 deg quoted in literature by more than 2 sigma. Conversely, it is shown that the white dwarf’s mass range obtained from spectroscopic measurements is compatible with my experimental range, but not for i=35 deg. As a consequence, my estimate of i yields an orbital separation of a=(0.59±0.05)R_⊙ and an equilibrium temperature of BD of T _eq=(2087±154) K which differ by 10% and 4%, respectively, from the corresponding values for i=35 deg.     

RECENT DEVELOPMENTS IN DEBRIS FLOW RESEARCH IN ITALY

ＲＥＣＥＮＴＤＥＶＥＬＯＰＭＥＮＴＳＩＮＤＥＢＲＩＳＦＬＯＷＲＥＳＥＡＲＣＨＩＮＩＴＡＬＹＭａｒｃｈｉＬｏｒｅｎｚｏ；ＴｅｃｃａＰｉａＲ．（ＩｎｓｔｉｔｕｔｅｆｏｒＰｒｅｖｅｎｔｉｏｎｏｆＨｙｄｒｏｌｏｇｉｃａｌａｎｄＧｅｏｌｏｇｉｃａｌＨａｚａｒｄ...     

Dendrogeomorphic dating of rockfalls on low‐latitude,high‐elevation slopes: Rodadero,Iztaccíhuatl volcano,Mexico

Dynamics and rates of rockfalls have been repeatedly studied in mountain environments with archival records as well as lichenometric, radiocarbon or dendrogeomorphic approaches. In this study, we test the potential of conifers growing at a low‐latitude, high‐elevation site as a dendrogeomorphic tool to reconstruct to calendar dates associated rockfall activity. Analysis is based on tree‐ring records of Mexican mountain pine (Pinus hartwegii Lindl.) growing at timberline [~4000 m above sea level (a.s.l.)] and at the runout fringe of a north–northeast (NNE)‐facing slope of the dormant Iztaccíhuatl volcano (Mexico), which is subject to frequent rockfalls. The potential and limitations of tree‐ring data are demonstrated based on 67 rockfall impacts dated in the increment‐ring series of 24 trees since ad 1836. While findings of this paper are site‐specific, the study clearly shows the potential of dendrogeomorphic approaches in extra‐Alpine, low‐latitude environments and for the understanding of rockfall processes in space and time. Copyright © 2011 John Wiley & Sons, Ltd.     

Global sensitivity analysis through polynomial chaos expansion of a basin-scale geochemical compaction model

We present a model-driven uncertainty quantification methodology based on sparse grid sampling techniques in the context of a generalized polynomial chaos expansion (GPCE) approximation of a basin-scale geochemical evolution scenario. The approach is illustrated through a one-dimensional example involving the process of quartz cementation in sandstones and the resulting effects on the dynamics of the vertical distribution of porosity, pressure, and temperature. The proposed theoretical framework and computational tools allow performing an efficient and accurate global sensitivity analysis (GSA) of the system states (i.e., porosity, temperature, pressure, and fluxes) in the presence of uncertain key mechanical and geochemical model parameters as well as boundary conditions. GSA is grounded on the use of the variance-based Sobol indices. These allow discriminating the relative weights of uncertain quantities on the global model variance and can be computed through the GPCE of the model response. Evaluation of the GPCE of the model response is performed through the implementation of a sparse grid approximation technique in the space of the selected uncertain quantities. GPCE is then be employed as a surrogate model of the system states to quantify uncertainty propagation through the model in terms of the probability distribution (and its statistical moments) of target system states.