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.     

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.     

Germination and seedling development of switchgrass and smooth bromegrass exposed to 2,4,6-trinitrotoluene

It is estimated that explosives contaminate approximately 0.82 million cubic metres of soil at former military installations throughout the US; major contaminants often include 2,4,6-trinitrotoluene (TNT) and its degradation products. At some sites, phytoremediation may be a viable option to incineration or other costly remediation treatments. Grasses may be particularly suited for remediation because of their growth habit and adaptability to a wide range of soil and climate conditions. We characterized the effects of TNT on germination and early seedling development of switchgrass and smooth bromegrass to evaluate their potential use on contaminated sites. Switchgrass and smooth bromegrass seeds were germinated in nutrient-free agar containing 0 to 60 mg TNT litre(-1). Smooth bromegrass germination decreased as TNT concentration increased, while switchgrass germination was unaffected by TNT. Concentrations up to 15 mg TNT litre(-1) did not affect switchgrass root growth rate, but bromegrass root growth was reduced at TNT concentrations above 7.5 mg litre(-1). At 7.5 mg TNT litre(-1), however, shoot growth rate was reduced in both species. Examination at 20-fold magnification revealed switchgrass radicles were unaffected by TNT, while smooth bromegrass radicles appeared slightly swollen. Results indicate switchgrass is more tolerant of TNT than smooth bromegrass, but the establishment of both species may be limited to soil containing less than 50 mg kg(-1) of extractable TNT.     

Three-dimensional patterns of moisture, water repellency, bromide and pH in a sandy soil

Soil water repellency might lead to preferential flow of water and solutes through the unsaturated zone of soils. To study this process in a water repellent sandy field soil, a bromide tracer had been applied on a 2.2 m long and 0.4 m wide plot. The bromide application rate was 8 g/m², and the plot was sampled using 100 cm³ steel cylinders after 52 mm of rainfall in 12 days. A total of seven layers were sampled to a depth of 74 cm. Each layer was sampled at 240 locations in a 40 by 6 grid. All samples were used for the determination of soil water content, degree of actual and potential water repellency, bromide concentration and pH. The spatial distribution of these properties was visualized three-dimensionally and compared. The degree of water repellency, bromide concentration, and pH distribution bore close resemblance to the fingered flow induced soil water content distribution. The degree of potential water repellency was relatively low in places with such fingers. Actual water repellency occurred between the fingers at the dry spots. Bromide was not found, or only in very low concentrations, in such places. Bromide depth profiles clearly indicated the occurrence of diverging flow in the wetter subsoil. Most likely, manuring activities during the last decades resulted in relatively high pH values in the topsoil, and in the subsoil along the recurring fingered flow pathways.     

Chlorohydrocarbons, PCB congeners, polychlorodioxins, furans and dibenzothiophenes in pine needles in the vicinity of a metal reclamation plant

Chlorohydrocarbons, PCB congeners, polychlorodioxins, furans and dibenzothiophenes in pine needles in the vicinity of a metal reclamation plant were analyzed by GC/ECD and GC/MS. Wax and the rest of the needles were analyzed separately. As a rule the concentrations of -HCH (0.5–13.6 ng/g), γ-HCH (0.4–7.3 ng/g), HCB (0.2–3.4 ng/g), PCB congeners (0.2–67 ng/g), PCDDs and PCDFs were higher in the older needles. The ratio of the concentration in the wax to the concentration in the rest of the needles was higher in the younger needles. The concentrations of PCB congeners, TeCDDs and TeCDFs were higher in the needles collected in the area nearest to the plant. The samples, obviously, contained tri- and tetrachlorodibenzothiophenes but these were not determined quantitatively due to interfering peaks in GC/MS.     

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.     

A laboratory exposure procedure for screening pulp and paper mill effluents for the potential of causing increased mixed function oxidase activity in fish

To better understand the relationships between pulp manufacturing processes and mixed function oxidase (MFO) enzyme induction in fish, a practical and standardized exposure procedure is required. This study was undertaken to develop a laboratory-based exposure procedure to quantify the relative MFO induction potencies of different types of pulp and paper mill effluents. One major consideration in developing the procedure was to ensure that the protocol was practical so that tests could be performed in a short time, with small volumes of effluents and using simple experimental conditions. A series of concentration-response and time-course experiments were conducted to find the minimum time and effluent concentration which could distinguish the ability of different effluents to cause significant MFO induction in rainbow trout in the laboratory. Experiments were also conducted to determine the effects of biotic and abiotic factors such as loading density, fish size and feeding regime. This study showed that the exposure of rainbow trout in the laboratory to 10% concentration of secondary-treated effluent for 96 h caused significant increases in hepatic MFO activity. The magnitude of MFO induction was comparable to other field and laboratory observations. While fish size, loading density and feeding regime were found to affect the test results, consistent responses within a laboratory using this protocol are possible, provided that these factors are standardized. Therefore, the short-term exposure approach described in this paper could be a relevant tool for assessing the ability of different types of pulp and paper mill effluents to cause MFO induction in fish.     

NLEAP model simulation of climate and management effects on N leaching for corn grown on sandy soil

The Nitrate Leaching and Economic Analysis Package (NLEAP) model was used to evaluate effects of climate and N fertility on nitrate leaching from a 3-yr field experiment of continuous corn (Zea mays L.). Half of the plots were randomly chosen to be either nonirrigated or irrigated (based upon calculated potential evapotranspiration). Three replications of nitrogen (N) fertility (56, 112 and 224 kg ha⁻¹) were used. Soil was a Hecla sandy loam to loamy sand (Pachic Udic Haploboroll). Soil and climate data were from the upper Midwest U.S.A. database for NLEAP. On-site data were used in the model when available.This study shows that NLEAP is capable of integrating data collected for nonirrigated and irrigated conditions on sandy soil for a wide range of N treatments and predicting the nitrate available for leaching (NAL). Precipitation distribution and amount were different in each year. Calculated NAL provided an excellent indicator of potential nitrate leaching hazard. NLEAP output showed that leaching of residual N on this sandy soil is very sensitive to early-spring precipitation. The NLEAP model provided valuable insights concerning effects of climate and N and irrigation management on N leaching. To obtain optimum yields while minimizing nitrate leaching, this study indicates the need to use soil and plant-tissue testing, post-emergence N-fertilizer application, and modem irrigation-scheduling technology. Also, use of the NLEAP model along with field-plot experiments provide additional important information concerning timing of N-leaching events relative to climate and an additional assessment of the effectiveness of fertilizer-N management decisions.