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.     

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.     

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.     

Management options to limit nitrate leaching from grassland

Nitrate leaching can be reduced by the adoption of less intensive grassland systems which, though requiring a greater land area to achieve the same agricultural output, result in less nitrate leaching per unit of production than do intensively managed grasslands. The economic penalties associated with reductions in output can be partly offset by greater reliance on symbiotic nitrogen fixation and the use of clover-based swards in place of synthetic N fertilisers. Alternatively, specific measures can be adopted to improve the efficiency of nitrogen use in intensively managed systems in order to maintain high outputs but with reduced losses. Controls should take account of other forms of loss and flows of nitrogen between grassland and other components of the whole-farm system and, in most instances, should result in an overall reduction in nitrogen inputs. Removing stock from the fields earlier in the grazing season will reduce the accumulation of high concentrations of potentially leachable nitrate in the soil of grazed pastures but will increase the quantity of manure produced by housed animals and the need to recycle this effectively. Supplementing grass diets with low-nitrogen forages such as maize silage will reduce the quantity of nitrogen excreted by livestock but may increase the potential for nitrate leaching elsewhere on the farm if changes to cropping patterns involve more frequent cultivation of grassland. Improved utilisation by the sward of nitrogen in animal excreta and manures and released by mineralisation of soil organic matter will permit equivalent reductions to be made in fertiliser inputs, provided that adequate information is available about the supply of nitrogen from these non-fertiliser sources.     

Growth and nutrition of Quercus rubra L. seedlings and mature trees after three seasons of ozone exposure

Seedling growth and nutritional status have been shown to be sensitive to ozone, but the influence of multi-season ozone exposure on mature tree growth and nutrition has not been examined. To determine if seedlings and mature trees were similarly affected by ozone exposure, growth and nutrient concentrations in northern red oak (Quercus rubra L.) 4-year-old seedlings and 32-year-old mature trees were examined after treatment with subambient, ambient and twice ambient concentrations of ozone for three growing seasons. SUM00 values summed over the three growing seasons were 147, 255 and 507 ppm-h, respectively, for the subambient, ambient and twice ambient exposures. For mature trees, no influence of ozone treatment on lower stem diameter growth, stem growth within the mid-canopy and foliar biomass was observed. Seedling height was increased by ozone, but biomass and diameter were unaffected. A reduction in the specific leaf weight of leaves in response to ozone coincident with the loss of recurrent flushing was observed in seedlings. Ozone exposure reduced foliar nitrogen concentrations and increased woody tissue nutrient concentrations in seedlings and mature trees at the end of the third growing season. These results suggest an influence of ozone on retranslocation processes in seedlings and mature trees.     

Biomonitoring of air pollutants from traffic and industries employing Ramalina ecklonii (Spreng.) Mey. and Flot. in Córdoba, Argentina

The lichen Ramalina ecklonii (Spreng.) Mey. and Flot. was transplanted to 29 biomonitoring sites in the southeastern area of Córdoba, Argentina and tested for chlorophyll a, phaeophytin a, conjugated dienes concentration, malondialdehyde, soluble protein content and sulfur accumulation. The biomonitoring sites were determined according to (i) vehicular traffic levels, and (ii) industrial density, i.e. number and type of industries (small and medium) close to each of the sites. Each of the two groups were then broken down into three categories which provided a basis for performance analysis and quantification of the chemical parameters in the biomonitor. A pollution index (P.I.) was calculated based on the ratio of phaeophytin a to chlorophyll a and ratio of sulfur, malonaldehyde and conjugated dienes in transplanted specimens to sulfur, malonaldehyde and conjugated dienes in the freshly picked specimens. Significant differences were observed in sulfur content and P.I. in lichen samples that had been transplanted to sites with different vehicular traffic levels. At the same time, significant differences in the phaeophytin a concentration, phaeophytin a/chlorophyll a ratio and P.I. were observed at sites characterized by different levels of industrial density (all with low-to-medium traffic).     

The impact of SO2 and SO2 + ascorbic acid treatments on growth and partitioning of dry matter in Trigonella foenum-graecum L

To study the impact of SO(2) and SO(2) + ascorbic acid on growth and partitioning of dry matter in Trigonella foenum-graecum L., two-week-old plants were exposed to SO(2) for 2 h daily over a 42 day period. One of the exposed sets was treated with ascorbic acid. Plants were grown in a wire house and unexposed plants were used as controls for comparison. The parameters measured, such as dry weights of leaf, stem and root per plant, were found to be lower in the exposed sets than in the controls. The reductions were greater in dry weights of stem and root as compared with weights of leaves, indicating that the partitioning of the dry matter was altered. Greater amounts of soluble sugars and starch in the leaves of exposed plants, compared with the stem, also revealed that translocation was hampered. Reductions were greater in fruiting than in flowering, suggesting that fruit abortion was high. Although ascorbic acid treatment could mitigate the effect of SO(2), the differences were not found to be statistically significant. Significant changes were seen in fruit yield, suggesting that the effect of ascorbic acid is cumulative. The impact of SO(2) and SO(2) + ascorbic acid on partitioning of dry matter to different 'sinks' is discussed.     

Organic carbon concentration profiles in recent cave sediments: records of agricultural pollution or diagenesis?

Recent (<7 years old) cave sediments in Speedwell Cavern, Derbyshire, show an approximately exponential decay of organic carbon with depth. This phenomenon was thought to be due to one of two causes: (i) changing agricultural practice within the catchment feeding the cave, especially the increased use of sewage sludge and animal slurry as fertilizer; (ii) a relatively constant organic carbon concentration over time in the input sediment, with subsequent carbon mineralization during diagenesis. Carbon isotope composition of the organic material and the evolution of H/C ratio with depth indicate that the latter hypothesis is correct and that the profiles result from microbial diagenesis, not increased organic carbon inputs. By comparison with sediment of known (7 years) age, temporal decay constants for organic matter can be derived; these lie between rates previously determined for organic matter decomposition in marine sediments and soils. The H/C ratio of organic matter can be modelled as a function of time and proceeds in a similar fashion to soil organic material.     

Effect of ozone on net photosynthesis in oat (Avena sativa) and duckweed (Lemna gibba)

Short exposure to ozone depressed photosynthesis in both oat and duckweed at concentrations above 140 microg m(-3) and 300 microg m(-3), respectively. The effect on exposed oat flag leaves was age-dependent, with maximum susceptibility to ozone 10-20 days after emergence of the panicle. In duckweed, photosynthesis was more sensitive to differences in ozone concentration than to differences in duration of exposure.