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.

No abstract

Clay minerals are layer type aluminosilicates that figure in terrestrial biogeochemical cycles, in the buffering capacity of the oceans, and in the containment of toxic waste materials. They are also used as lubricants in petroleum extraction and as industrial catalysts for the synthesis of many organic compounds. These applications derive fundamentally from the colloidal size and permanent structural charge of clay mineral particles, which endow them with significant surface reactivity. Unraveling the surface geochemistry of hydrated clay minerals is an abiding, if difficult, topic in earth sciences research. Recent experimental and computational studies that take advantage of new methodologies and basic insights derived from the study of concentrated ionic solutions have begun to clarify the structure of electrical double layers formed on hydrated clay mineral surfaces, particularly those in the interlayer region of swelling 2:1 layer type clay minerals. One emerging trend is that the coordination of interlayer cations with water molecules and clay mineral surface oxygens is governed largely by cation size and charge, similarly to a concentrated ionic solution, but the location of structural charge within a clay layer and the existence of hydrophobic patches on its surface provide important modulations. The larger the interlayer cation, the greater the inf luence of clay mineral structure and hydrophobicity on the configurations of adsorbed water molecules. This picture extends readily to hydrophobic molecules adsorbed within an interlayer region, with important implications for clay-hydrocarbon interactions and the design of catalysts for organic synthesis.

No abstract

X-ray diffraction (XRD) and Mn K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy were combined to elaborate a structural model for phyllomanganates (layer-type Mn oxide) lacking 3D ordering (turbostratic stacking). These techniques were applied to a sample produced by a common soil and freshwater bacterium (Pseudomonas putida) and to two synthetic analogs, δ-MnO 2 and "acid birnessite", obtained by the reduction of potassium permanganate with MnCl 2 and HCl, respectively. To interpret the diffraction and spectroscopic data, we applied an XRD simulation technique utilized previously for wellcrystallized birnessite varieties, complementing this approach with single-scattering-path simulations of the Mn K-edge EXAFS spectra. Our structural analyses revealed that all three Mn oxides have an hexagonal layer symmetry with layers comprising edge-sharing Mn 4+ O 6 octahedra and cation vacancies, but no layer Mn 3+ O 6 octahedra. The proportion of cation vacancies in the layers ranged from 6 to 17 %, these vacancies being charge-compensated in the interlayer by protons, alkali metals, and Mn atoms, in amounts that vary with the phyllomanganate species and synthesis medium. Both vacancies and interlayer Mn were

Abstract--Monte Carlo (MC) simulations of molecular structure in the interlayers of 2:1 Na-saturated clay minerals were performed to address several important simulation methodological issues. Investigation was focused on monolayer hydrates of the clay minerals because these systems provide a severe test of the quality and sensitivity of MC interlayer simulations. Comparisons were made between two leading models of the water-water interaction in condensed phases, and the sensitivity of the simulations to the size or shape of the periodically-repeated simulation cell was determined. The results indicated that model potential functions permitting significant deviations from the molecular environment in bulk liquid water are superior to those calibrated to mimic the bulk water structure closely. Increasing the simulation cell size or altering its shape from a rectangular 21.12 A x 18.28 ~ x 6.54 ~ cell (about eight clay mineral unit cells) had no significant effect on the calculated interlayer properties.

No abstract

The surface horizons of two arid‐zone field soils that had received amendments of either liquid or dried, anaerobically digested sewage sludge for 4 years were sampled to determine the forms of selected trace metals in the solid phase. The soils had been amended with sludge twice annually at rates of 0, 22.5, 45.0, or 90.0 tons · ha−1 · year−1. Barley and sorghum had been grown on the soils in randomized experimental plots. The soil samples were analyzed for total Ni, Cu, Zn, Cd, and Pb and were fractionated by sequential extraction to estimate the quantities of these metals in “exchangeable,” “sorbed,” “organic,” “carbonate,” and “sulfide” forms.The total contents of the five metals in the two field soils were governed by the total content of the metals in the sludges applied and by the rate of sludge application. The accumulation of metals in the surface horizons of field plots receiving liquid sludge was less than that in the plots receiving composted sludge, possibly because of a lesser reduction in soil bulk density resulting from sludge applications. The percentage of the total metal content in exchangeable and sorbed forms was very low, averaging between 1.1 and 3.7% for all of the metals regardless of the type of soil, the form of sludge applied, or the sludge application rate. The application of sludge tended to reduce the sulfide fraction and to increase the organic and carbonate fractions of all five trace metals. At the highest rate of sludge application, the predominant forms of the metals were: Ni, sulfide; Cu, organic; and Zn, Cd, and Pb, carbonate.