A new concept: the use of neutrally-buoyant microemulsions for DNAPL remediation

Even in the absence of mobilization of dense nonaqueous phase liquid (DNAPL), the microemulsion that forms when the surfactant solubilizes a dense contaminant such as trichloroethylene will be more dense than water and tends to migrate downward. This paper addresses the issue of migration with a new concept: surfactant enhanced aquifer remediation at neutral buoyancy. Laboratory results of surfactant remediation in two-dimensional model aquifers show that downward migration of microemulsion containing solubilized dense contaminants can be reduced to an acceptable level, even in the absence of capillary barriers in the aquifer. One model experiment was designed to exhibit a small degree of vertical migration and full capture of the microemulsion at the extraction well. The second experiment was designed to demonstrate the effect of large buoyancy forces that lead to excessive downward migration of the microemulsion. Density measurements of aqueous solutions containing sodium dihexyl sulfosuccinate surfactant, isopropanol, trichloroethylene, and sodium chloride are presented. A companion paper presents the results of the flow and transport calculations needed for this approach to surfactant flooding.     

Biochemical response of Norway spruce (Picea abies (L.) Karst.) towards 14-month exposure to ozone and acid mist: effects on amino acid, glutathione and polyamine titers

Two clones of Norway spruce were exposed to elevated ozone levels (100 microg m(-3) with episodes of 130-360 microg m(-3)) in combination with acidic mist (pH 3.0) for two vegetation periods. The plants did not exhibit any visible injury, but levels of several amino acids and polyamines were altered in comparison with control plants (50 microg m(-3) ozone, mist of pH 5.6), the changes being pronounced in clone 14. Total free amino acids as well as methionine titers were increased in clone 14. Asparagine was significantly increased in clone 11 and less so in clone 14. Arginine, which comprised more than 50% of the free amino acids in spruce needles, was not changed by the exposure regime applied. Reduced glutathione was significantly increased in all clones/soil/needle age combinations (average increase 50%). Free soluble putrescine was enhanced by 50-200% in clone 14, but remained unchanged in clone 11. Conjugated putrescine was significantly, and conjugated spermidime was slightly, increased in both clones, whereas other polyamines did not responde to the treatment.     

Effects of ozone, acid mist and soil characteristics on clonal Norway spruce (Picea abies (L.) Karst.)--an introduction to the joint 14 month tree exposure experiment in closed chambers

This paper introduces a series of publications referring to a single 14-month laboratory study testing the hypothesis that the recent decline of Norway spruce (Picea abies (L.) Karst.) at higher elevations of the Bavarian Forest and comparable forests in medium-range mountains and in the calcareous Alps is caused by an interaction of elevated ozone concentrations, acid mist and site-specific soil (nutritional) characteristics. The effect of climatic extremes, a further important factor, was not included as an experimental variable but was considered by testing of the frost resistance of the experimental plants. Results of these individual studies are presented and discussed in the following 14 papers. Plants from six pre-selected clones of 3-year-old Norway spruce (Picea abies (L.) Karst.) were planted in April 1985 in an acidic soil from the Bavarian Forest, or a calcareous soil from the Bavarian Alps. After a transition period, plants were transferred, in July 1986, into four large environmental chambers and exposed for 14 months to an artificial climate and air pollutant regime based on long-term monitoring in the Inner Bavarian Forest. The climatic exposure protocol followed realistic seasonal and diurnal cycles (summer maximum temperature, 26 degrees C; total mean temperature, 9.8 degrees C; winter minimum, -14 degrees C; mean relative humidity, 70%; maximum irradiance, 500 W m(-2); daylength summer maximum, 17 h; winter minimum, 8 h). Plants were fumigated with ozone, generated from pure oxygen (control: annual mean of 50 microg m(-3); pollution treatment: annual mean of 100 microg m(-3) with 68 episodes of 130-360 microg m(-3) lasting 4-24 h), and background concentrations of SO(2) (22 microg m(-3)) and NO(2) (20 microg m(-3)); windspeed was set at a constant 0.6 m s(-1). Plants were additionally exposed to prolonged episodes of misting at pH 5.6 (control) and pH 3.0 (treatment). Simulation of the target climatic and fumigation conditions was highly reliable and reproducible (temperature +/-0.5 degrees C; rh+/-10%; ozone+/-10 microg m(-3);SO(2) and NO(2)+/-15 microg m(-3)).     

Trace elements in soil and biota in confined disposal facilities for dredged material

We studied the relation of trace element concentrations in soil to those in house mice (Mus musculus), common reed (Phragmites australis) and ladybugs (Coccinella septempunctata at five disposal facilities for dredged material. The sites had a wide range of soil trace element concentrations, acid soils and a depauperate fauna. They were very poor wildlife habitat because they were dominated by the common reed. Bioassay earthworms exposed to surface soils from three of the five sites died, whereas those exposed to four of five soils collected a meter deep survived, presumably because the deeper, unoxidized soil, was not as acid. Concentrations of Ni and Cr in the biota from each of the sites did not seem to be related to the concentrations of the same elements in soil. Although Pb, Zn and Cu concentrations in biota were correlated with those in soil, the range of concentrations in the biota was quite small compared to that in soil. The concentrations of Pb detected in mice were about as high as the concentrations previously reported in control mice from other studies. Mice from the most contaminated site (530 ppm Pb in soil) contained only slightly more Pb (8 ppm dry wt) than did mice (2-6 ppm dry wt) from sites containing much less Pb (22-92 ppm in soil). Despite the acid soil conditions, very little Cd was incorporated into food chains. Rather, Cd was leaching from the surface soil. We concluded that even the relatively high concentrations of trace elements in the acid dredged material studied did not cause high concentrations of trace elements in the biota.     

Effects of ozone on yield, growth, and root starch concentrations of two alfalfa (Medicago sativ A L.) cultivars

Ozone (O3) is considered to be a major air pollutant that affects the yield of several sensitive crop species. Its concentration may reach phytotoxic levels several times during the growing season in Eastern Canada. This study was initiated to evaluate the O3 effects on alfalfa, a major crop species. The objective was to compare the yield and growth parameters of the main alfalfa cultivar used in Québec, Apica, to a cultivar more tolerant to O3, Team. Effects on root starch concentrations were also examined as this parameter is an important indicator of alfalfa perennity. The results obtained have shown that the forage yield of Apica was more reduced by O3 during two growing seasons than the yield of Team. For O3 concentrations of 20 to 40 nl liter(-1), yield reductions were 14-26% for Apica and 0-20% for Team. Whereas Apica could be considered more susceptible to O3 than Team, the latter has shown contrasting responses from year to year. This fact suggests that the mechanisms involved in O3-tolerance could be modulated by environmental conditions. At low O3 levels, Apica has shown reduced root growth in terms of dry matter and length. However, contrary to the current hypothesis that O3 would affect more root than shoot growth, we were unable to show a consistent alteration of the biomass allocation between the two. Ozone seems to reduce globally the growth of the whole plants. The greater O3-tolerance of Team could partly be associated to its capacity to maintain more leaves, to delay their senescence, or to keep a larger leaf:stem ratio under increasing levels of O3. At the end of the two growing seasons, the amount of starch reserves stored below ground was shown to be reduced by the current O3 levels. This reduction was mainly associated with a decrease in root biomass under O3 stress. This result support the hypothesis that O3 may accelerate alfalfa decline under field conditions.     

The influence of particle surface characteristics on pollutant metal uptake by cells

The phosphatic mineral, hydroxyapatite, and two ion exchange resins have been used as artificial sediment particles. The surface properties of these materials have been studied using the Langmuir adsorption isotherm to calculate the binding capacity (B(max)) and the adsorption constant (K(L)) for zinc and cadmium ions. Mussels (Mytilus edulis) were fed on the particles and their digestive glands were subsequently removed and subjected to cell fractionation. The supernatant fraction was used to determine cytosol metal levels as a measure of the materials absorbed from the ingested particles. The level of cytosol zinc and cadmium was correlated with the K(L) values of the artificial sediments. It is suggested that phagocytosis of sediment particles plays an important part in transferring pollutants into benthic organisms and that the efficiency of this process is related to the adsorption coefficient of the particle surfaces.     

Effects of degree of water saturation on dispersivity and immobile water in sandy soil columns

Three natural nonaggregated soil samples, with similar grain-size distributions, have been used to determine the dispersive behavior of porous media under steady, saturated and unsaturated flow conditions. Tritium was used as a tracer and was found to have no sorption on the solid matrix. Generated breakthrough curves (BTCs) for the unsaturated experiments were symmetrical with no evidence of tailing. The unsaturated experiments for two of the soils were adequately described by considering all the water in the pore volume as mobile. However, about 10% of the pore water, independent of the degree of saturation, was found to be immobile in the case of the third soil during unsaturated flow. For this soil, there was no mass transfer between the two water regions, indicating that the immobile water is essentially isolated from the flowing water fraction. For all three soils, dispersivity under unsaturated conditions was found to be higher, independent of the degree of water saturation, than the value determined for the saturated experiments. This is inconsistent with what would be expected from the simple bundle-of-capillary-tubes model and does not agree well with a more sophisticated conceptualization of the porous medium. The data, however, clearly indicate a wider range in pore-water velocities when these soils are desaturated.     

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.     

Earthworm communities along a gradient of urbanization

Earthworms were studied at six sites along a gradient of urbanization and their relations with several soil abiotic factors were determined. Concentrations of heavy metals, calcium and magnesium in earthworms and in soils were measured by atomic absorption spectroscopy. Strong negative correlations were detected between earthworm density and soil concentrations of cadmium and magnesium. Earthworm biomass was negatively correlated with lead, copper and zinc, and positively correlated with the distance from the centre of the city. High concentrations of Cd and Zn (concentration factors 49 and 32) were accumulated by earthworms in contrast to those of Cu and Pb (2 and 1). Relations between worm and soil concentrations of heavy metals, Ca and Mg are discussed.     

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.