Biodegradation of juvenoid diastereoisomers: radio-HPLC and MS analysis

Microbial degradation of two diastereoisomeric forms 2 and 3 of a selected juvenoid (insect juvenile hormone bioanalog), ethyl N-{2-{4-[(2-hydroxycyclohexyl)methyl]phenoxy}ethyl}carbamate was studied and the degradation products analyzed. Degradation experiments were performed using simple modeling under laboratory conditions. A Candida sp. strain T1, isolated from soil, was chosen as a biodegradation species. Radiolabeling of the studied compounds 2 and 3 was used in combination with radio-HPLC and MS analysis to increase the limits of detection, monitoring and isolation of trace quantities of the products of degradation and/or transformation. Resulting from the microbial processes using 2 or 3 as source compounds, three identical products (4-6) of their biodegradation were produced. Compound 2 also afforded two additional products (7, 8). Radio-HPLC analysis and separation, and subsequent MS analysis of the degradation mixtures resulted in identification of the degradation products. The degree and the rate of biodegradation of 2 and 3 were analyzed after 1, 3 and 7 days from the beginning of the experiment.     

Effect of pH control at the anode for the electrokinetic removal of phenanthrene from kaolin soil

Polycyclic aromatic hydrocarbon (PAH)-contaminated soils exist at numerous sites, and these sites may threaten public health and the environment because many PAH compounds are toxic, mutagenic, and/or carcinogenic. PAHs are also hydrophobic and persistent, so conventional remediation methods are often costly or inefficient, especially when the contaminants are present in low permeability and/or organic soils. An innovative technique, electrokinetically enhanced in situ flushing, has the potential to increase soil-solution-contaminant interaction and PAH removal efficiency for low permeability soils; however, the electrolysis reaction at the anode may adversely affect the remediation of low acid buffering capacity soils, such as kaolin. Therefore, the objective of this study was to improve the remediation of low acid buffering soils by controlling the pH at the anode to counteract the electrolysis reaction. Six bench-scale electrokinetic experiments were conducted, where each test employed one of three different flushing solutions, deionized water, a surfactant, or a cosolvent. For each of these solutions, tests were performed with and without a 0.01 M NaOH solution at the anode to control the pH. The test using deionized water with pH control generated a higher electroosmotic flow than the equivalent test performed without pH control, but the electroosmotic flow difference between the surfactant and cosolvent tests with and without pH control was minor compared to that observed with the deionized water tests. Controlling the pH was beneficial for increasing contaminant solubilization and migration from the soil region adjacent to the anode, but the high contaminant concentrations that resulted in the middle or cathode soil regions indicates that subsequent changes in the soil and/or solution chemistry caused contaminant deposition and low overall contaminant removal efficiency.     

Dechlorination of pentachloroethane by commercial Fe and ferruginous smectite

Short-term experiments were conducted to investigate the effect of a commercial Fe and an iron-bearing clay mineral, ferruginuous smectite (SWa-1), on the degradation of pentachloroethane (PCA). After 3 h of contact time, SWa-1 catalyzed PCA dehydrochlorination to tetrachloroethene (PCE, 65% conversion), whereas commercial Fe promoted PCA stepwise dechlorination via dehydrochlorination (approximately 40% conversion) and subsequent PCE hydrogenolysis to trichloroethene (TCE). The addition of unaltered SWa-1 to commercial Fe led to a complete inhibition on TCE production, whereas the addition of reduced SWa-1 barely resulted in a 30% decrease.     

Kinetics of heat-assisted persulfate oxidation of methyl tert-butyl ether (MTBE)

The kinetics of heat-assisted persulfate oxidation of methyl tert-butyl ether (MTBE) in aqueous solutions at various pH, temperature, oxidant concentration and ionic strength levels was studied. The MTBE degradation was found to follow a pseudo-first-order decay model. The pseudo-first-order rate constants of MTBE degradation by persulfate (31.5 mM) at pH 7.0 and ionic strength 0.11 M are approximately 0.13 x 10(-4), 0.48 x 10(-4), 2.4 x 10(-4) and 5.8 x 10(-4) S(-1) at 20, 30, 40 and 50 degrees C, respectively. Under the above reaction conditions, the reaction has an activation energy of 24.5 +/- 1.6 kcal/ mol and is influenced by temperature, oxidant concentration, pH and ionic strength. Raising the reaction temperature and persulfate concentration may significantly accelerate the MTBE degradation. However, increasing both pH (over the range of 2.5-11) and ionic strength (over the range of 0.11-0.53 M) will decrease the reaction rate. Reaction intermediates including tert-butyl formate, tert-butyl alcohol, acetone and methyl acetate were observed. These intermediate compounds were also degraded by persulfate under the experimental conditions. Additionally, MTBE degradation by persulfate in a groundwater was much slower than in phosphate-buffer solutions, most likely due to the presence of bicarbonate ions (radical scavengers) in the groundwater.     

Development and demonstration of an explicit lumped-parameter biofilter model and design equation incorporating monod kinetics

Biofiltration is an economical air pollution control (APC) technology, particularly suitable for the treatment of air-streams having high flow rates and low concentrations of volatile organic compounds (VOCs). This technology utilizes enzymatic catalysis at ambient conditions to mineralize such pollutants to CO2, H2O, and salts. A pilot-scale study conducted for more than 4 years investigated the development of a new biofiltration technology employing trickle bed air biofilters (TBABs). Following the completion of this experimental study, additional data analysis was performed to develop a simple lumped-parameter biofilter model, assuming first-order kinetics. This model related the observed biofilter performance to the principle independent physical, thermodynamic, and biochemical parameters. The initial model has subsequently been expanded to incorporate Monod kinetics. In this paper, the development and use of the final explicit lumped-parameter biofilter model and design equation, incorporating Monod kinetics, are presented. To facilitate the application of this model, practical procedures are also presented for the determination of VOC solubility, VOC biokinetic Monod parameters, and the maximum practical biofilter inlet VOC concentration.     

Long-term trends and spatial variability in nitrate leaching from alpine catchment-lake ecosystems in the Tatra Mountains (Slovakia-Poland)

Relationships between catchment characteristics of 31 alpine lakes and observed trends in lake water concentrations of nitrate were evaluated in the Tatra Mountains. Nitrate concentrations increased from background levels <4 microeql(-1) in the 1930s to maxima (up to 55 microeql(-1)) in the 1980s, after which they declined to 4-44 microeql(-1) by the late 1990s. In-lake nitrate concentrations correlated negatively with parameters characterising catchment-weighted mean pools (CWM; kgm(-2)) of soil, i.e. with percent land cover with meadow and soil depth, and positively with grade of terrain, annual precipitation, and the highest elevation in the catchment. The CWM pool of soil and annual precipitation explained together 65% of the current spatial variability in nitrate concentrations. Denitrification and direct N deposition on surface area explained 14% of the variability. Increased atmospheric N deposition and declining net N retention in soils were responsible for long-term changes in nitrate concentrations. Long-term decline in %N retention in soils decreased along with the estimated decline in C:N ratios (from 21 to 18 on average during the last 70 years). An empirical model linking nitrate concentrations in different types of alpine Tatra Mountain lakes to four independent variables (CWM soil pool, annual precipitation, increased N deposition, and average trend in soil C:N ratios) explained 80% of the observed spatial and temporal nitrate variability over the period 1937-2000.     

Transformation and adsorption of Fenamiphos, f. sulfoxide and f. sulfone in molokai soil and simulated movement with irrigation

The ban of commonly used soil fumigants, DBCP and EDB, for control of nematodes in pineapple fields has prompted investigations into a non-fumigant nematicide, fenamiphos (Nemacur^®). The transformation and adsorption in soil of fenamiphos and its transformation products, f. sulfoxide and f. sulfone were studied in the laboratory. Fenamiphos adsorption on soil exceeded that of f. sulfoxide and f. sulfone. F. sulfoxide, however, was the most persistent. A one-dimensional simulation model was used to assess the impact of transformation and adsorption on the mobility and distribution of fenamiphos and f. sulfoxide in soil. Simulated results showed that fenamiphos stayed in the topsoil and transformed rapidly to f. sulfoxide. Because of the persistence and mobility of f. sulfoxide, this metabolite leached rapidly and significant amounts remained in the soil. This suggests that for times exceeding three weeks, f. sulfoxide may be the dominant compound providing nematode control in drip-irrigated pineapple.