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The charged surfaces of micaceous minerals, especially illite, regulate the mobility of the major radioisotopes of Cs (134Cs, 135Cs, 137Cs) in the geosphere. Despite the long history of Cs adsorption studies, the nature of the illite surface sites remains incompletely understood. To address this problem, we present atomistic simulations of Cs competition with Na for three candidate illite adsorption sites - edge, basal plane, and interlayer. Our simulation results are broadly consistent with affinities and selectivities that have been inferred from surface complexation models. Cation exchange on the basal planes is thermodynamically ideal, but exchange on edge surfaces and within interlayers shows complex, thermodynamically non-ideal behavior. The basal planes are weakly Cs-selective, while edges and interlayers have much higher affinity for Cs. The dynamics of NaCs exchange are rapid for both cations on the basal planes, but considerably slower for Cs localized on edge surfaces. In addition to new insights into Cs adsorption and exchange with Na on illite, we report the development of a methodology capable of simulating fully-flexible clay mineral nanoparticles with stable edge surfaces using a well-tested interatomic potential model.

The workability of fresh Portland cement (PC) concrete critically depends on the reaction of the cubic tricalcium aluminate (C3A) phase in Ca- and S-rich pH >12 aqueous solution, yet its rate-controlling mechanism is poorly understood. In this article, the role of adsorption phenomena in C3A dissolution in aqueous Ca-, S-, and polynaphthalene sulfonate (PNS)-containing solutions is analyzed. The zeta potential and pH results are consistent with the isoelectric point of C3A occurring at pH ∼12 and do not show an inversion of its electric double layer potential as a function of S or Ca concentration, and PNS adsorbs onto C3A, reducing its zeta potential to negative values at pH >12. The S and Ca K-edge X-ray absorption spectroscopy (XAS) data obtained do not indicate the structural incorporation or specific adsorption of SO42- on the partially dissolved C3A solids analyzed. Together with supporting X-ray ptychography and scanning electron microscopy results, a model for C3A dissolution inhibition in hydrated PC systems is proposed whereby the formation of an Al-rich leached layer and the complexation of Ca-S ion pairs onto this leached layer provide the key inhibiting effect(s). This model reconciles the results obtained here with the existing literature, including the inhibiting action of macromolecules such as PNS and polyphosphonic acids upon C3A dissolution. Therefore, this article advances the understanding of the rate-controlling mechanism in hydrated C3A and thus PC systems, which is important to better controlling the workability of fresh PC concrete.

The aqueous chemistry of water films confined between clay mineral surfaces remains an important unknown in predictions of radioelement migration from radioactive waste repositories. This issue is particularly important in the case of long-lived anionic radioisotopes (129I , 99TcO4 , 36Cl) which interact with clay minerals primarily by anion exclusion. For example, models of ion migration in clayey media do not agree as to whether anions are completely or partially excluded from clay interlayer nanopores. In the present study, this key issue was addressed for Cl using MD simulations for a range of nanopore widths (6 to 15 Å) overlapping the range of average pore widths that exists in engineered clay barriers. The MD simulation results were compared with the predictions of a thermodynamic model (Donnan Equilibrium model) and two pore-scale models based on the Poisson-Boltzmann equation under the assumption that interlayer water behaves as bulk liquid water. The simulations confirmed that anion exclusion from clay interlayers is greater than predicted by the pore-scale models, particularly at the smallest pore size examined. This greater anion exclusion stems from Cl being more weakly solvated in nano-confined water than it is in bulk liquid water. Anion exclusion predictions based on the PoissonBoltzmann equation were consistent with the MD simulation results, however, if the predictions included an ion closest approach distance to the clay mineral surface on the order of 2.0 0.8 Å. These findings suggest that clay interlayers approach a state of complete anion exclusion (hence, ideal semi-permeable membrane properties) at a pore width of 4.2 +/- 1.5 Å.

Irrigation with treated wastewater is expected to increase significantly in California during the coming decade as a way to reduce the impact of drought and mitigate water transfer issues. To ensure that such wastewater reuse does not result in unacceptable impacts on soil permeability, water quality guidelines must effectively address sodicity hazard. However, current guidelines are based on the sodium adsorption ratio (SAR) and thus assume that potassium (K) and magnesium (Mg), which often are at elevated concentrations in recycled wastewaters, pose no hazard, despite many past studies to the contrary. Recent research has established that the negative effects of high K and Mg concentrations on soil permeability are substantial and that they can be accounted for by a new irrigation water quality parameter, the cation ratio of structural stability (CROSS), a generalization of SAR. We show that CROSS, when suitably optimized, correlates strongly with a standard measure of soil permeability reduction for an agricultural soil leached with winery wastewater, and that it can be incorporated directly into existing irrigation water quality guidelines by replacing SAR.

Recent microcosm studies have revealed that fluoroquinolone (FQ) antibiotics can have ecotoxicological impacts on photosynthetic organisms, but little is known about the mechanisms of toxicity. We employed a combination of modeling and experimental techniques to explore how FQs may have these unintended secondary toxic effects. Structure-activity analysis revealed that the quinolone ring and secondary amino group typically present in FQ antibiotics may mediate their action as quinone site inhibitors in photosystem II (PS-II), a key enzyme in photosynthetic electron transport. Follow-up molecular simulations involving nalidixic acid (Naldx), a nonfluorinated quinolone with a demonstrated adverse impact on photosynthesis, and ciprofloxacin (Cipro), the most commonly used FQ antibiotic, showed that both may interfere stereochemically with the catalytic activity of reaction center II (RC-II), the pheophytin-quinone-type center present in PS-II. Naldx can occupy the same binding site as the secondary quinone acceptor (Q(B)) in RC-II and interact with amino acid residues required for the enzymatic reduction of Q(B). Cipro binds in a somewhat different manner, suggesting a different mechanism of interference. Fluorescence induction kinetics, a common method of screening for PS-II inhibition, recorded for photoexcited thylakoid membranes isolated from Cipro-exposed spinach chloroplasts, indicated that Cipro interferes with the transfer of energy from excited antenna chlorophyll molecules to the reaction center in RC-II ([Cipro] >or= 5 microM in vitro and >or=10 microM in vivo) and thus delays the kinetics of photoreduction of the primary quinone acceptor (Q(A); [Cipro] >or= 0.6 microM in vitro). Spinach plants exposed to Cipro exhibited severe growth inhibition characterized by a decrease in both the synthesis of leaves and growth of the roots ([Cipro] >or= 0.5 microM in vivo). Our results thus demonstrate that Cipro and related FQ antibiotics may interfere with

We analyzed the possibility of introducing a single stochastic scaling parameter a to describe the spatial variability of soil hydraulic properties, using the soil hydraulic properties of the Hamra field (Russo and Bresler 1981) and the Panache field (Nielsen, Biggar, and Erh 1973). In the traditional approach (Peck, Luxmoore, and Stolzy 1977; Russo and Bresler 1980; Warrick, Mullen, and Nielsen 1977), sets of scaling factors are estimated from the h(s) and K(s) functions. For "perfectly similar media," the two sets of a should be identical. Even though the sets of a in these studies were found to be correlated (table 2), they possessed different statistical properties, and were not identical. Results of structural analyses of the sets of a from the two fields suggested that the spatial structures of the two a-sets are quite distinct, reflecting the different spadal behavior of the h(θ) and the K(θ) functions. Moreover, there was poor correlation between the uncorrelated residuals of the a-sets, indicating that part of the high correlation between the a-sets found in earlier work must stem from the presence of an undetected drift and from correlation between nearby measurements. Under field conditions, the saturated hydraulic conductivity is controlled by the flow of water through large structural voids (macropores), which drain at very small negative values of water pressure. Because of this, we tried eliminating Ks by using relative hydraulic properties instead of the hydraulic properties themselves to estimate the scaling factor sets. For the Hamra field, for which we assumed that the hydraulic properties could be described by the model of Brooks and Corey (1964), we found the resultant sets of scaling factors to be highly correlated (R2 = 0.996) with the same spatial structure, but with slightly different variance. By examining the relationships between the two a-sets implied by the Brooks and Corey (1964) model we saw that (1) in general, both sets wi

A critical examination of published data obtained primarily from recent nuclear magnetic resonance spectroscopy, X-ray absorption near-edge structure spectroscopy, electrospray ionization-mass spectrometry, and pyrolysis studies reveals an evolving new view of the molecular structure of soil humic substances. According to the new view, humic substances are collections of diverse, relatively low molecular mass components forming dynamic associations stabilized by hydrophobic interactions and hydrogen bonds. These associations are capable of organizing into micellar structures in suitable aqueous environments. Humic components display contrasting molecular motional behavior and may be spatially segregated on a scale of nanometers. Within this new structural context, these components comprise any molecules intimately associated with a humic substance, such that they cannot be separated effectively by chemical or physical methods. Thus biomolecules strongly bound within humic fractions are by definition humic components, a conclusion that necessarily calls into question key biogeochemical pathways traditionally thought to be required for the formation of humic substances. Further research is needed to elucidate the intermolecular interactions that link humic components into supramolecular associations and to establish the pathways by which these associations emerge from the degradation of organic litter.

Several experiments to determine the apparent activation energies of several processes contributing to water movement in soils and to develop a theory of soil water movement in terms of the molecular physics of the several contributing processes are reported., See also AD-270840 dated Sep 1961.