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.     

Intercomparison between TRIO-EF and IMPACT codes with reference to experimental strontium migration data

This work presents an intercomparison exercise between two geochemical migration codes, TRIO-EF (an object-oriented finite element code) and IMPACT (a chemical engineering code using mixing cells in series). The predictions of the two codes are compared with the reference experimental results obtained in a previous study of strontium transport in soil columns. This simulated geochemical system is well documented and includes ion exchange and dissolution-precipitation reactions. The solution transport is simulated by a one-dimensional advection-dispersion model. The predictions of TRIO-EF and IMPACT are both in good agreement with the experimental results. However, slight differences can be observed between the two codes, especially when concentration discontinuities are involved, such as precipitation fronts or changes in boundary conditions. These discrepancies between the two codes can mainly be attributed to the different discretisation approaches.     

Predicting change in fish mercury concentrations following reservoir impoundment

Fish mercury concentrations frequently increase after impoundment of a reservoir. Soil flooding releases organic matter and nutrients, providing food to bacterial communities that methylate inorganic mercury. Methylation and bioaccumulation are the primary pathways for mercury accumulation in fish. We investigated if changes in fish mercury concentrations could be predicted from the change in reservoir size. Data for three fish species, northern pike (Esox lucius), walleye (Stizostedion vitreum), and lake whitefish (Coregonus clupeaformis) from reservoirs in northern Manitoba and northern Quebec were used to evaluate four simple models of change in mercury with change in flooded area. For three additional fish species, all primary carnivores, the preferred model consisted of a single exponential enrichment term. This model successfully predicted two cases not used in model development-one with a large change in area and one with a small change in area. Models with good predictive skill can be developed when the underlying dynamics are known.     

Imposex in the commercial snail Bolinus brandaris in the northwestern Mediterranean

A survey of the degree of imposex in populations of the commercial muricid Bolinus brandaris (L.) was carried out at six locations along the Catalan Coast (NW Mediterranean). Imposex was found to be a widespread phenomenon; the occurrence of a penis was observed in all females studied with the exception of those from St. Carles (South of Catalunya) where only 37% were affected. Other indices such as Relative Penis Length (RPL) and Vas Deferens Sequence (VDS) were applied; RPL varied from 4.5% in St. Carles--the least affected area--to 29.8% in the vicinity of Barcelona; similar results were obtained for VDS. Tissue organotin residues ranged from 6 to 140 ng g(-1) w.w. as Sn. Despite legislation restricting the use of tributyltin (TBT) in antifouling paints, this paper evidences the occurrence of organotin pollution far from the source, with levels of both TBT and triphenyltin (TPhT) high enough to cause environmental concern.     

Miscible fluid displacement stability in unconfined porous media:: Two-dimensional flow experiments and simulations

In situ flushing groundwater remediation technologies, such as cosolvent flushing, rely on the stability of the interface between the resident and displacing fluids for efficient removal of contaminants. Contrasts in density and viscosity between the resident and displacing fluids can adversely affect the stability of the displacement front. Petroleum engineers have developed techniques to describe these types of processes; however, their findings do not necessarily translate directly to aquifer remediation. The purpose of this laboratory study was to investigate how density and viscosity contrasts affected cosolvent displacements in unconfined porous media characterized by the presence of a capillary fringe. Two-dimensional flow laboratory experiments, which were partially scaled to a cosolvent flushing field experiment, were conducted to determine potential implications of flow instabilities in homogeneous sand packs. Numerical simulations were also conducted to investigate the differential impact of fluid property contrasts in unconfined and confined systems. The results from these experiments and simulations indicated that the presence of a capillary fringe was an important factor in the displacement efficiency. Buoyant forces can act to carry a lighter-than-water cosolvent preferentially into the capillary fringe during displacement of the resident groundwater. During subsequent water flooding, buoyancy forces can act to effectively trap the cosolvent in the capillary fringe, contributing to the inefficient removal of cosolvent from the aquifer.     

Hydrological and geochemical factors affecting leachate composition in municipal solid waste incinerator bottom ash: Part I: The hydrology of Landfill Lostorf, Switzerland

The objective of the investigation of the municipal solid waste incinerator (MSWI) bottom ash landfill, Landfill Lostorf, was to determine the residence time of water in the landfill and the flow paths through the landfill. Over a period of 22 months, measurements of rainfall, landfill discharge and leachate electrical conductivity were recorded and tracer experiments made. Over the yearly period 1995, approximately 50% of the incident rainfall was measured in the discharge. An analysis of single rain events showed that in winter, 90–100% of rainfall was expressed in the landfill discharge, whereas in summer months, the value was between 9 and 40% depending on the intensity of the rain event. The response to rainfall was rapid. Within 30–100 h, approximately 50% of water discharged in response to a rain event had left the landfill. The discharge was less than 4 l/min for approximately 50% of the measurement periods. Qualitative tracer studies with fluorescein, pyranine and iodide clearly showed the existence of preferential flow paths. This was further substantiated by quantitative tracer studies of single rain events using / ratios and electrical conductivity measurements. The proportion of rainwater passing directly through the landfill was found to be between 20 and 80% in summer months and around 10% in winter months. The difference has been ascribed to the water content in the landfill. The average residence time of the water within the landfill has been estimated to be roughly 3 years and this water is the predominant component in the discharge over a yearly period.     

Natural phillipsite as a matrix for a slow-release formulation of oxamyl

The performance of phillipsite as a matrix for slow-release formulation of oxamyl [N,N-dimethyl-2-methylcarbamoyl-oxymino-2-(methylthio)acetamide] was tested. The adsorption kinetics followed a first-order law, and the adsorption isotherm fitted well in a two-surface Langmuir model, suggesting a double mechanism of interaction between oxamyl and the sorbent. The sorption mechanism, studied by FTIR, provided two fractions of oxamyl. The first one is sorbed on the mineral surface, linked by H-bonding, and the second one is constituted by a multilayer of oxamyl molecules linked by a water bridge between them. The release kinetics of oxamyl from a substratum zeolite-oxamyl also follows a first-order law, with two stages that correspond to both fractions of oxamyl previously detected.     

Marginal bleaching of thalli of Rhizocarpon as evidence for acid rain in the Norra Storfjället, Sweden

Recent lichen surveys in the foreland of The Syterb?cken glacier reveal that the crustose lichens, principally species of Rhizocarpon section Rhizocarpon, exhibit marginal bleaching, readily distinguishable from normal pigmented forms. The largest elliptical thallus of Rhizocarpon measured 290 mm maximum diameter on a bedrock outcrop beyond the margin of Little Ice Age moraines in the upper Syterb?cken Valley. Many small and large thalli of Rhizocarpon suffered damage to the periphery of individual thalli. We examine here some of the possible hypotheses explaining these occurrences. Among others, these are bedrock lithology, ice crystal blasting, long-term snowbank cover, ultraviolet exposure and acid rain. While at this time none of the possibilities can be ruled out entirely, acid rain would appear to be at least one of the factors involved. Acid rain, which is known to produce a soil pH as low as 3.3 in the field area, appears to provide a high input of H(+) ions that the lichen algal component cannot withstand. However, the lack of similar effects on associated foliose or fruticose forms raises the possibility that perhaps two or more factors specific to the environment of Rhizocarpon are operating.     

Fractionation of fulvic acids: characteristics and complexation with copper

Two fulvic acid samples isolated from Suwannee river (International Humic Substance Society) and Feeitsuey reservoir were subjected to gel filtration chromatography (GFC) for molecular size fractionation. The GFC-eluted samples were separated into three groups corresponding to the molecular weight ranges: < 220, 220-1000, and 1000-4000. Fluorescence quenching techniques were employed for determining the conditional stability coefficient and kinetic parameters of copper complexation with the three fractions of fulvic acids. Experimental conditions were pH 6, 5 x 10(-5)m total copper and 5 mg C litre(-1) of fulvic acids. The conditional stability coefficients of the fulvic acid fractions were in the order of 0.9-3.3 x 10(5)m(-1), and the forward and reverse rate constants were in the order of 6.9-12.4 x 10(3)m(-1) s(-1) and 3.5-8.0 x 10(-2) s(-1). Information could be useful in modelling copper transport in the hydrosphere.