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.     

Buffer zone widths for honeybees from ground and aerial spraying of insecticides

The relative field hazards of insecticides to honeybees have been estimated by considering intrinsic toxicity levels and field application rates. This approach is extended here to a consideration of buffer zones downwind of sprayed areas by estimating the distance at which bees would encounter an LD(50) dose from spray drift. 'LD(50) distances' are determined for both ground and aerial spraying of ground crops in Britain using published data on spray deposition under various weather conditions. For ground spraying at low wind speeds (< or =3 m s(-1)), this zone of risk is up to 5 m for the great majority of compounds. Aerial spraying in unstable atmospheric conditions appears to produce drift deposits of about the same order of magnitude as from ground spraying at wind speeds of about 4 m s(-1), with maximum LD(50) distances of < or =40 m for chlorpyrifos, fenitrothion and triazophos. For aerial spraying in stable atmospheric conditions these distances would be much greater. Pieris brassicae larvae are contrasted with honeybees in their relative sensitivities to insecticides and consequent LD(50) distances.     

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)).     

90-day oral toxicity of ziram: a thyrostatic and hepatotoxic study

Ziram, a dithiocarbamate fungicide, is extensively used in crop protection. Daily oral doses of ziram (5 and 25 mg kg(-1) day(-1)) for 30, 60 and 90 days produced significant mortality in male rats. The fungicide also caused a significant increase in the thyroid:body weight ratio, histological changes, and a reduced activity of thyroid (125)I uptake and protein bound (125)I. However, the animals did not show any change in the clinical enzyme profile of the liver, serum and brain. It is believed that ETU, the degradation product of ziram and a known antithyroid compound, is the causative agent for the high mortality, as well as for the pronounced thyrostatic and hepatotoxic effects found in the experimental animals.     

Pollen germination is impeded by tap water

Pollen germination in vitro is totally inhibited in tobacco (Nicotiana tabacum) and other species if tap water is used to prepare the germination medium. This effect is already fully present if tap water accounts for only 25% of the medium. Furthermore, the pollen grains deteriorate rapidly and the culture medium turns yellowish-brown. The water toxicity is not caused by one or several compounds regularly monitored by the water authorities but can be removed by ion exchange purification. Although the factor(s) responsible for the inhibition were not identified, the study clearly shows the presence of such a contaminant in three different Orange County (Southern California) water wells. The fact that a fundamental botanical process like pollen germination is inhibited by a factor in drinking water not included in water quality control causes some general health concern. In addition, crop yield might be largely reduced if overhead spray irrigation with this water is utilized. The experiments also suggest that pollen germination in vitro could serve as a sensitive and simple bioassay for water quality.     

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.     

Effects of elevated CO2, nitrogen supply and tropospheric ozone on spring wheat-II. Nutrients (N, P, K, S, Ca, Mg, Fe, Mn, Zn)

CO(2) enrichment is expected to alter leaf demand for nitrogen and phosphorus in plant species with C(3) carbon dioxide fixation pathway, thus possibly causing nutrient imbalances in the tissues and disturbance of distribution and redistribution patterns within the plants. To test the influence of CO(2) enrichment and elevated tropospheric ozone in combination with different nitrogen supply, spring wheat (Tritium aestivum L. cv. Minaret) was exposed to three levels of CO(2) (361, 523, and 639 microl litre(-1), 24 h mean from sowing to final harvest), two levels of ozone (28.4 and 51.3 nl litre(-1)) and two levels of nitrogen supply (150 and 270 kg ha(-1)) in a full-factorial design in open-top field chambers. Additional fertilization experiments (120, 210, and 330 kg N ha(-1)) were carried out at low and high CO(2) levels. Macronutrients (N, P, K, S, Ca, Mg) and three micronutrients (Mn, Fe, Zn) were analysed in samples obtained at three different developmental stages: beginning of shoot elongation, anthesis, and ripening. At each harvest, plant samples were separated into different organs (green and senescent leaves, stem sections, ears, grains). According to analyses of tissue concentrations at the beginning of shoot elongation, the plants were sufficiently equipped with nutrients. Elevated ozone levels neither affected tissue concentrations nor shoot uptake of the nutrients. CO(2) and nitrogen treatments affected nutrient uptake, distribution and redistribution in a complex manner. CO(2) enrichment increased nitrogen-use efficiency and caused a lower demand for nitrogen in green tissues which was reflected in a decrease of critical nitrogen concentrations, lower leaf nitrogen concentrations and lower nitrogen pools in the leaves. Since grain nitrogen uptake during grain filling depended completely on redistribution from vegetative pools in green tissues, grain nitrogen concentrations fell considerably with severe implications for grain quality. Ca, S, Mg and Zn in green tissues were influenced by CO(2) enrichment in a similar manner to nitrogen. Phosphorus concentrations in green tissues, on the other hand, were not, or only slightly, affected by elevated CO(2). In stems, 'dilution' of all nutrients except manganese was observed, caused by the huge accumulation of water soluble carbohydrates, mainly fructans, in these tissues under CO(2) enrichment. Whole shoot uptake was either remarkably increased (K, Mn, P, Mg), nearly unaffected (N, S, Fe, Zn) or decreased (Ca) under CO(2) enrichment. Thus, nutrient cycling in plant-soil systems is expected to be altered under CO(2) enrichment.