Three-fluid retention in porous media involving water, PCE and air

A classical way to obtain three-fluid retention curves in porous media from measured two-fluid retention curves is based on the Leverett concept, which states that the total volumetric liquid content in a water-wet porous medium, containing water, a nonaqueous-phase liquid (NAPL) and air, is a function of the capillary pressure across the interface between the continuous NAPL and air. This functional relationship results from the assumed condition that in a three-fluid porous medium, the intermediate wetting fluid spreads over the water-air interface. Application of Leverett's concept may not be valid, however, for nonspreading NAPLs like perchloroethylene (PCE). This paper discusses measurements of both PCE-air and water-PCE-air retention curves using a long vertical column in conjunction with a dual-energy gamma radiation system. The data indicate that the Leverett concept was applicable only until a critical PCE saturation had been reached.     

Development of a continuously stirred flow cell for investigating sorption mass transfer

This paper introduces a new reversible-flow design for a continuously stirred reactor used to study sorption mass transfer in soil and solvent systems. The stirred reactor has potential advantages over conventional packed column or batch reactors because it isolates intraparticle sorption rate limitations from advective-dispersive transport, yet allows changes to flux through the reactor for analysis of sorption kinetics under dynamic conditions. Previously, stirred reactors have often failed due to clogging of sediment on the effluent frit. The reverse-flow backwashing design allows longer life and higher confidence in maintaining mixed conditions than previous designs. Mass transfer 'rate coefficients estimated from stirred and column experiments are compared; both techniques produced results consistent with a published correlation. The data also show that fitted sorption mass transfer coefficients can be strongly dependent on the choice of equilibrium partition coefficient (i.e. batch or first-moment derived values), and that the conventional two-site sorption kinetics model fails to accurately predict sorption mass transfer in the presence of changing solvent velocity through the reactor.     

Colloid migration in symmetrical non-uniform fractures: particle tracking in three dimensions

A three-dimensional model for the migration of colloids in a saturated fracture is presented, which considers the motion of colloids as a result of advection and diffusion, as well as colloid-surface interactions at the fracture walls. This model is successfully incorporated into a three-dimensional particle tracking algorithm that tracks particles within a continuum and allows consideration of the migration of colloids in symmetrical, three-dimensional, non-uniform fractures. The framework is general enough to incorporate non-local interactions that provide colloid motion relative to the fluid. The algorithm is verified against classical Taylor dispersion, and its generalization to a sorbing phase, in a uniform fracture and shows excellent agreement with theory. A simple, non-uniform fracture that has an analytically tractable velocity field is also considered, and both quantitative and qualitative comparisons are made with the uniform fracture case. The modelling of more complex fracture geometries is also discussed and a particular case is implemented within the particle tracking framework.     

Surface complexation modeling of Yb(III) sorption and desorption on hematite and alumina

Sorption and desorption of Yb(III) were studied on hematite and on alumina using a surface complexation model. The experimental methodology was conceived to allow an analysis of the data using a constant capacitance model. The FITEQL code was used for the calculations.The experimental results tend to show reversibility of sorption when the surface loading is small, and irreversibility when the surface loading is high. Surface complexation modeling gives a good interpretation of these two phenomena, taking into account hydroxylation of the surface complexes. In these two cases, it is possible to describe sorption and desorption curves with the same surface stoichiometries and the same surface complexation constants. The existence of these surface complexes depends on the pH of the solution, surface loading, and reaction direction.     

A new approach for modelling potential effects in cation adsorption onto binary (hydr) oxides

The current approach for modelling ion adsorption onto binary (hydr)oxides using homogeneous surface complexation models involves the assumption of either an ideal mixture of the two surfaces (i.e. two surface sites on one surface) or a patchwise surface (i.e. two surfaces with one surface site on each surface). As the physical truth should be between these two limiting cases, a model which assumes a patchwise surface constituted of three patches is proposed. Two patches represent the distinct (hydr)oxides, and the third one a mixture of these distinct (hydr)oxides. Using the diffuse layer model, the three approaches are applied to literature data for Cd adsorption onto binary mixtures of alumina-coated silica at total constant Cd concentration and varying amounts of alumina coatings. For Cd adsorption onto these binary (hydr)oxide systems, the new approach explains the observed potential effects. The proposed model, which contains two additional adjustable parameters in terms of site concentrations or one adjustable parameter in terms of specific surface area, is more successful than the two limiting cases. The new model is then validated by predicting Ca and Zn behaviour on the same binary (hydr)oxide system.     

Do aquatic effects or human health end points govern the development of sediment-quality criteria for nonionic organic chemicals ?

The equilibrium partitioning theory may be used to describe the partitioning of nonionic organic chemicals between water, sediment, and aquatic biota. This paradigm was employed to compare the relative magnitudes of organic carbon-normalized sediment-quality criteria that are intended to protect either benthic organisms from the direct toxic effects of sediment-associated chemicals or humans from the indirect health effects posed by the ingestion of contaminated aquatic animals. Comparison of calculated sediment-quality criteria for a variety of hydrophobic chemicals suggests that human health-based end points often result in more restrictive criteria than aquatic effects-based values. Review of published field data indicates that the equilibrium partitioning paradigm may, depending on contaminant class, either over- or underestimate the extent to which sediment-associated contaminations are bioaccumulated. Despite the limitations of adopting this simple theory for criteria development, calculations reveal that regulatory decisions involving sediments contaminated with such chemicals may be dictated by human health concerns if current risk assessment methodologies are applied.     

Biodegradation of crosslinked acrylic polymers by a white-rot fungus

Two synthetic superabsorbent crosslinked acrylic polymers were mineralized by the white-rot fungusPhanerochaete chrysosporium. The amount of polymer converted to CO₂ increased as the amount of polymer added to the cultures increased. In the presence of sufficiently large amounts of the superabsorbents, such that all of the culture fluid was absorbed and a gelatinous matrix was formed, the fungus still grew and mineralization was observed. Neither the polymers, nor their degradation products were toxic to the fungus. While the rates of mineralization were low, all of the polymers incubated in the liquid fungal cultures were completely depolymerized to water soluble products within 15–18 days. The depolymerization of the polymers was observed only in nitrogen limited cultures of the fungus which secrete the lignin degradation system, however, the water soluble products of depolymerization were mineralized in both nutrient limited and sufficient cultures of the fungus. The rate of mineralization of the depolymerized metabolites was more than two times greater in nutrient sufficient cultures. Following longer incubation periods, most (> 80 %) of the radioactivity was recovered in the fungal mycelial mat suggesting that carbon of the polymer had been converted to fungal metabolites.