Coupling permanganate oxidation with microbial dechlorination of tetrachloroethene.

For sites contaminated with chloroethene non-aqueous-phase liquids, designing a remediation system that couples in situ chemical oxidation (ISCO) with potassium permanganate (KMnO4) and microbial dechlorination may be complicated because of the potentially adverse effects of ISCO on anaerobic bioremediation processes. Therefore, one-dimensional column studies were conducted to understand the effect of permanganate oxidation on tetrachloroethene (PCE) dechlorination by the anaerobic mixed culture KB-1. Following the confirmation of PCE dechlorination, KMnO4 was applied to all columns at a range of concentrations and application velocities to simulate varied distances from oxidant injection. Immediately following oxidation, reductive dechlorination was inhibited; however, after passing several pore volumes of sterile growth medium through the columns after oxidation, a rebound of PCE dechlorination activity was observed in every inoculated column without the need to reinoculate. The volume of medium required for a rebound of dechlorination activity differed from 1.1 to 8.1 pore volumes (at a groundwater velocity of 4 cm/d), depending on the specific condition of oxidant application.     

Response of fluctuating asymmetry to arsenic toxicity: support for the developmental selection hypothesis

The effect of exposure to sodium arsenite during development was tested on adult fluctuating asymmetry (FA) in sternopleural bristle number, bristle number, body size and survivorship in Drosophila melanogaster. Three genetic strains of flies were used, CT-106, PVM and Oregon-R, and arsenite concentrations ranged from relatively mild, sub-lethal doses, to concentrations with pronounced negative effects on survivorship. At arsenite concentrations of 1.0 and 0.125 mM, mortality was on average 38% greater than in controls, and surviving flies emerged significantly smaller and had fewer bristles than controls. Neither the effect of arsenite or the genotype x environment interaction on asymmetry were significant. However, given the high mortality, any increase in FA could have been masked by the outcome of developmental selection against developmentally unstable phenotypes. We tested for this effect by contrasting FA values between (1) flies reared at the highest concentrations used previously, (2) flies reared at sub-lethal dosage, and (3) controls. Positional fluctuating asymmetry (PFA), which is expected to be a sensitive indicator of underlying developmental stability, was significantly reduced among flies reared at the highest concentration, and at which flies suffered significant mortality. Moreover, the slope of the regression relating mean PFA to emergence per bottle was significantly positive. These data support the hypothesis that developmental selection occurred in this experiment, and that the expected positive relationship between asymmetry and stress may be altered when the stressor eliminates individuals from the population. In contrast, FA of flies reared at sub-lethal dosage did not differ from that in controls, a result that fails to support the hypothesis that arsenite disrupts developmental stability. Our results call for caution in FA-based biomonitoring, especially of potentially lethal forms of stress, because in the presence of developmental selection, and under the common assumption that FA should increase under stress, erroneous conclusions may be drawn about the health and well being of a population. It is suggested that FA-based biomonitoring efforts integrate the use of FA with other bioindicators, and experimentally validate any expected FA-stress relationship before attempting to infer the presence of environmental stress.     

Chemical valorization of forest and agricultural by-products. Obtention, chemical characteristics, and mechanical behavior of a novel family of hydrophobic films

Esterification of hemicelluloses of the xylan family was performed in order to produce hydrophobic films. Acylation reactions were carried out with lauroyl chloride in the N,N-dimethylacetamide/lithium chloride homogeneous system using 4-dimethylaminopyridine as activator and were induced by microwave irradiation. In the experimental conditions used, 108 and 172% mass ratios were obtained for the dodecyl-grafted xylan and heteroxylan, respectively. The degrees of substitution (DS) were 1.3 (maximum 2) for xylan and 1.2 (maximum 2.1) for heteroxylan. These products were further characterized by FT-IR spectroscopy. The mechanical and thermomechanical behavior of this new family of hydrophobic films were analyzed and compared to those obtained from cellulose with a similar DS by the means of tensile tests. Our results indicate that the dodecyl-grafted xylan film presents the best rigidity-resistance to traction ratio.     

Comparative toxicity of Solvent Yellow 33 [2-(2′-quinolinyl)-1,3-indandione] and Solvent Green 3 (1,4-di-p-toluidinoanthraquinone) dyes to freshwater organisms

Solvent Yellow 33 and a Solvent Green 3 mixture (30:70 mixture of Solvent Yellow 33 and Solvent Green 3) were not acutely toxic to seven of nine freshwater species when tested at the solubility limits of the dyes in freshwater. A solubility limit solution of the Solvent Green 3 mixture killed 50% of the rainbow trout tested for 96 h but was non-toxic when diluted by 50%. Both dyes caused a reduction in green algal growth at solubility limits. The Solvent Green 3 mixture was the most detrimental causing a 98–99% reduction in growth after 5 days of exposure.     

Toward a high-rate enhanced biological phosphorus removal process in a membrane-assisted bioreactor.

A membrane enhanced biological phosphorus removal (MEBPR) process was studied to determine the impact of hydraulic retention time (HRT) and solids retention time (SRT) on the removal of chemical oxygen demand (COD), nitrogen, and phosphorus from municipal wastewater. The MEBPR process was capable of delivering complete nitrification independent of the prevailing operating conditions, whereas a significant improvement in COD removal efficiency was observed at longer SRTs. In the absence of carbon-limiting conditions, the MEBPR process was able to achieve low phosphorus concentrations in the effluent at increasingly higher hydraulic loads, with the lowest HRT being 5 hours. The MEBPR process was also able to maintain optimal phosphorus removal when the SRT was increased from 12 to 20 days. However, at higher suspended solids concentrations, a substantial increase was observed in carbon utilization per unit mass of phosphorus removed from the influent. These results offer critical insights to the application of membrane technology for biological nutrient removal systems.     

Genetic effects of air pollution on forest tree species of the Carpathian Mountains

The effects of air pollution on the genetic structure of Norway spruce, European silver fir and European beech were studied at four polluted sites in Slovakia, Romania and Czech Republic. In order to reduce potential effects of site heterogeneity on the health condition, pair-wise sampling of pollution-tolerant and sensitive trees was applied. Genotypes of sampled trees were determined at 21 isozyme gene loci of spruce, 18 loci of fir and 15 loci of beech. In comparison with Norway spruce, fewer genetic differences were revealed in beech and almost no differentiation between pollution-tolerant and sensitive trees was observed in fir. In adult stands of Norway spruce, sensitive trees exhibited higher genetic multiplicity and diversity. The decline of pollution-sensitive trees may result thus in a gradual genetic depletion of pollution-exposed populations of Norway spruce through the loss of less frequent alleles with potential adaptive significance to altered stressing regimes in the future. Comparison of the subsets of sensitive and tolerant Norway spruce individuals as determined by presence or absence of discolorations ("spruce yellowing") revealed different heterozygosity at 3 out of 11 polymorphic loci.     

Impact of engine lubricant properties on regulated gaseous emissions of 2000-2001 model-year gasoline vehicles

The impact of the sulfur (S) content in lubricating oil was evaluated for four ultra-low-emission vehicles and two super-ultra-low-emission vehicles, all with low mileage. The S content in the lube oils ranged from 0.01 to 0.76%, while the S content of the gasoline was fixed at 0.2 ppmw. Vehicles were configured with aged catalysts and tested over the Federal Test Procedure, at idle and at 50-mph cruise conditions. In all testing modes, variations in the S level of the lubricant did not significantly affect the regulated gas-phase tailpipe emissions. In addition to the regulated gas-phase emissions, a key element of the research was measuring the engine-out sulfur dioxide (SO2) in near-real-time. This research used a new methodology based on a differential optical absorption spectrometer (DOAS) to measure SO2 from the lubricants used in this study. With the DOAS, the contribution of SO2 emissions for the highest-S lubricant was found to range from less than 1 to 6 ppm on a gasoline S equivalent basis over the range of vehicles and test cycles used. The development and operation of the DOAS is discussed in this paper.     

Investigations of nitrogen fluxes and pools on a limestone site in the Alps

In the North Tyrolean Limestone Alps a site was investigated over a four-year period (1998–2001) in order to assess the nitrogen saturation status, the nitrogen budget (quantification of the net uptake of nitrogen by the canopy and of the nitrogen mineralization, nitrogen uptake from roots and N₂O emission rates, proof of the origin of nitrate in the soil water with stable isotope analyses), and the effects of the actual nitrogen input on ground water quality. The main goals were to quantify the nitrogen input rate, the nitrogen pools in above-ground and below-ground compartments, nitrogen turnover processes in the soil as well as the output into the groundwater and into the atmosphere. The findings are based on continuous and discontinuous field measurements as well as on model results.While nitrogen input exceeded the Critical Loads of the WHO (1995), nitrogen deficiency and nutrient imbalances were verified by needle analyses. The atmospheric input of inorganic nitrogen was higher than the nitrogen output in 50 cm soil depth. A tracer experiment with¹⁵N helped to prove that not more than half of the applied nitrate could be discharged. This allows the conclusion that nitrogen is stored in the system and that the site cannot yet be said to be saturated with nitrogen. The same result was also obtained by modelling. In addition, it was proved that the nitrogen discharge did not stem from deposition but from processes within the system.     

Improving the extraction of tetrachloroethylene from soil columns using surfactant gradient systems

In this work, we extend the recently developed gradient approach for surfactant-enhanced remediation of dense non-aqueous phase liquid (DNAPL)-impacted sites. The goal of the gradient approach is to maximize the DNAPL solubilization capacity in swollen micelles (Type I aqueous microemulsions) while at the same time minimizing the potential for DNAPL mobilization. In this work, we introduce a modified version of the capillary/trapping curve that we refer to as the gradient curve to help interpret and/or design the gradient approach. The gradient curve presents the residual DNAPL saturation as a function of interfacial tension and microemulsion viscosity. This approach demonstrates that keeping a low viscosity of the microemulsion phase is not only important for keeping a low head loss during surfactant flooding but also to prevent oil mobilization. Eight microemulsion systems were evaluated in this research; these systems were evaluated based on their tetrachloroethylene (PCE) solubilization capacity, interfacial tension (IFT), viscosity, density, and coalescence kinetics. Two of these systems were chosen for evaluation in site-specific column tests using an increasing electrolyte gradient to produce a decreasing IFT/increasing solubilization gradient system. The column studies were conducted with media from Dover Air Force Base in Dover, DE. Both solubilized and mobilized DNAPL were quantified. During the column studies, we observed that substantial PCE was mobilized when the residual level of PCE in the column was significantly higher than the steady-state residual saturation level being approach (as predicted from the gradient curve). Four column studies were performed, three of which were used to asses the validity of the gradient curve in predicting the residual saturation after each gradient step. From these tests we observed that starting IFTs of less than 1 mN/m all produced the same mobilization potential. In the last column, we used an additional gradient step with an initial IFT above 1 mN/m to dramatically reduce the amount of PCE mobilize. Based on the good agreement between column results and projections based on the gradient curve, we propose this as a preferred method for designing gradient surfactant flushing systems.     

Inverse modeling of BTEX dissolution and biodegradation at the Bemidji, MN crude-oil spill site

The U.S. Geological Survey (USGS) solute transport and biodegradation code BIOMOC was used in conjunction with the USGS universal inverse modeling code UCODE to quantify field-scale hydrocarbon dissolution and biodegradation at the USGS Toxic Substances Hydrology Program crude-oil spill research site located near Bemidji, MN. This inverse modeling effort used the extensive historical data compiled at the Bemidji site from 1986 to 1997 and incorporated a multicomponent transport and biodegradation model. Inverse modeling was successful when coupled transport and degradation processes were incorporated into the model and a single dissolution rate coefficient was used for all BTEX components. Assuming a stationary oil body, we simulated benzene, toluene, ethylbenzene, m,p-xylene, and o-xylene (BTEX) concentrations in the oil and ground water, respectively, as well as dissolved oxygen. Dissolution from the oil phase and aerobic and anaerobic degradation processes were represented. The parameters estimated were the recharge rate, hydraulic conductivity, dissolution rate coefficient, individual first-order BTEX anaerobic degradation rates, and transverse dispersivity. Results were similar for simulations obtained using several alternative conceptual models of the hydrologic system and biodegradation processes. The dissolved BTEX concentration data were not sufficient to discriminate between these conceptual models. The calibrated simulations reproduced the general large-scale evolution of the plume, but did not reproduce the observed small-scale spatial and temporal variability in concentrations. The estimated anaerobic biodegradation rates for toluene and o-xylene were greater than the dissolution rate coefficient. However, the estimated anaerobic biodegradation rates for benzene, ethylbenzene, and m,p-xylene were less than the dissolution rate coefficient. The calibrated model was used to determine the BTEX mass balance in the oil body and groundwater plume. Dissolution from the oil body was greatest for compounds with large effective solubilities (benzene) and with large degradation rates (toluene and o-xylene). Anaerobic degradation removed 77% of the BTEX that dissolved into the water phase and aerobic degradation removed 17%. Although goodness-of-fit measures for the alternative conceptual models were not significantly different, predictions made with the models were quite variable.