Interphase mass transfer during chemical oxidation of TCE DNAPL in an aqueous system

The chemical oxidation of trichloroethene dense non-aqueous phase liquid by permanganate was studied in an aqueous system using micro-reaction/extraction vessels in a novel approach. Experiments were conducted at ambient temperature ( approximately 20 degrees C) under static and mixed conditions to evaluate the rate of TCE(DNAPL) dissolution as a function of permanganate concentration. Chemical oxidation by permanganate was shown to increase the rate of TCE(DNAPL) dissolution under static conditions and decrease the rate of dissolution under mixed conditions. The apparent inconsistency in results appears to result from the local deposition of a film at the DNAPL interface composed of manganese oxide solids as discovered through visual observation with the aid of a Goniometer. Data from interfacial deposition experiments suggest that the film formed rapidly and reached maturation within approximately 2 h with little or no growth occurring thereafter. A conceptual model of the reaction and mass transfer processes occurring at the DNAPL interface was proposed based on the experimental results.     

Polychlorinated biphenyls in Narragansett Bay surface sediments

Polychlorinated biphenyls (PCBs) were evaluated in 41 surface sediments collected from Narragansett Bay, RI in 1997-1998. Highest concentrations of total PCBs (1760 ng/g) were in rivers at the head of the bay and the values decreased southward toward the mouth of the bay, with elevated concentrations in some of the coves. The PCB levels in approximately 43% of the samples exceeded the effects range median (ERM) guideline [Environ. Manage. 19 (1995) 81] indicating possible adverse biological effects at these stations. Principal component analysis (PCA) of the surface sediment PCBs separated the Taunton River samples from the rest of the samples. This result suggests that this river has a different PCB composition and sources than the other areas investigated. It also showed that this river has a limited influence on other bay stations as the adjacent samples downstream did not have the same chemical signature. Congener ratios derived from the PCA were useful in distinguishing stations that had different sources of PCBs than the bulk of the bay sediments. Although Aroclor 1268 and 1270 accounted for <1% of all PCB production, their major components, CB206 and CB209, account for 3-6% of the CBs in most bay samples. This may reflect more local use of these Aroclor mixtures and/or be indicative of their relative stability, compared to less chlorinated mixtures. Using linear alkyl benzenes (LABs) as a marker for sewage derived PCBs suggested that up to 95% of the PCBs at the most contaminated sites in the Seekonk, Providence, and Taunton Rivers were sewage derived. This analysis also showed that there is a high background level (167 ng/g) of PCBs in the Seekonk and Providence River, while the Taunton River had a relatively low background level (23.7 ng/g). At the furthest stations south in the Providence River, the sewage derived PCBs only accounted for 23% of the total which suggests that PCB associated with sewage particles are rapidly deposited and are therefore not the most significant source of these compounds to the lower reaches of Narragansett Bay.     

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.