Reductive transformation of dieldrin under anaerobic sediment culture

A pathway of dieldrin transformation to aldrin by epoxide reduction was found in this study. Investigation of dieldrin degradation under anaerobic conditions was performed with a mixed culture containing indigenous microorganisms obtained from sediment of the Er-Jen River in Taiwan. During the incubation, the transformation of dieldrin to aldrin was analyzed by GC-ECD and GC-MS. Effects of incubation factors including dieldrin concentrations, incubation temperatures and kinds of carbon sources on the degradation of dieldrin were also studied. Original concentrations (from 0.5 to 10 microg ml(-1)) of dieldrin affect the transformation rate of dieldrin, and lower concentrations indicated the higher degradation rates. But once the concentration higher than 100 microg ml(-1), almost no degradation occurred. The optimal temperature for degradation in mixed culture was found at 40 degrees C in this study. Dieldrin transformation rates varied with the type of major carbon sources in the mixed culture and were in order of yeast extract > sodium acetate > glucose. In addition, the denaturing gradient gel electrophoresis (DGGE) fingerprint revealed that four microbials evolved in dieldrin-amended cultures, but not in the dieldrin-free cultures. Partial sequence of 16S rDNA for these four organisms exhibited 94-99% similarity to those of genera Clostridium, Acidaminobacter and an uncultured bacterial group. These results suggest that the four microbials might promote the dieldrin transformation.     

Dieldrin uptake by vegetable crops grown in contaminated soils

The aim of these trials was to study the distribution of dieldrin in soil and its translocation to roots and the aerial parts of vegetable crops grown in greenhouses and fields. The main objectives were to characterize dieldrin accumulation in plant tissues in relation to the levels of soil contamination; uptake capability among plants belonging to different species, varieties and cultivars. The presence of the contaminant was quantified by gas chromatography-electron capture detector (GC-ECD) and confirmed by gas chromatography-mass spectrometer (GC-MS). The results showed a translocation of residues in cucurbitaceous fruits and flowers confirming that zucchini, cucumber and melon are crops with high uptake capability. The maximum level of dieldrin residue at 0.01 mg/kg was found to be a threshold value to safeguard the quality production of cucurbits. Tomato, lettuce and celery were identified as substitute crops to grow in contaminated fields.     

Metabolic rate and uptake and loss of cadmium from food by the fish Noemacheilus barbatulus L. (stone loach)

Fish, Noemacheilus barbatulus (stone loach), of different body weights were used to study rates of uptake and loss of cadmium during and after dietary exposure. Fish were kept singly in a continuous-flow system, and fed tubificid worms. The worms had a range of cadmium levels, but all levels were below that needed to cause acute lethal toxicity in the fish. Body weight affected both the maintenance ration and the amount of food consumed ad libitum, but the exponent for body weight (0.78+/-0.04), relating body weight to food consumption, was unaffected by either temperature or the size of feeding ration. The cadmium content of the worms did not affect the size of the maintenance ration. Metal burden in fish changed rapidly both during and after exposure. After exposure, the cadmium burden of starved fish usually declined more rapidly than in fed fish. A 58-fold increase in cadmium content in the food produced a 28% increase of body burden in the fish, and there was no evidence for biomagnification. Maintenance ration and ration ad libitum and rates of uptake and loss of cadmium increased with temperature within the range 8-18 degrees C, but exposure to cadmium at 16 degrees C yielded a higher asymptotic body burden than either 8 degrees C or 18 degrees C. Rate constants for loss of cadmium after exposure appear to be lower than for loss during exposure. Rates of uptake and loss of cadmium vary with metabolic rate. A maximum in the rate of oxygen consumption was measured at 16 degrees C, above which the rate dropped, presumably due to stress. The exponent for body weight was unaffected by activity or temperature. Body weight of fish appeared to affect both the rates of uptake and loss of cadmium, and feeding rations and respiration to the same extent: body weight exponents were not dissimilar.     

Comparison of gas chromatography and immunoassay methods in measuring the distribution of dieldrin in rainbow trout tissues.

Studies have been conducted to determine the distribution of dieldrin in various tissues of rainbow trout when exposed to several dieldrin concentrations. Medium sized fish with an average weight and length of 195.4 +/- 30.5 g and 25.7 +/- 1.4 cm, respectively, were placed in groups of 6 in 300 L tanks containing purified and aerated water and maintained at 10 degrees C. Following an acclimatization period of 10 days, each group of fish was exposed to one of four dieldrin concentrations ranging from 50 to 80 ppb. After 24 hours, the fish were taken out of the tanks and sacrificed. The brain, gills, liver, muscles and skin were collected from each fish. Dieldrin was extracted from each tissue using SPE techniques and analyzed by both gas chromatography (GC) and enzyme linked immunosorbent assay (ELISA). Results of analyses by the two techniques were highly correlated. The results also showed that liver and skin tissues had the highest level of dieldrin residues. In comparing the means of the six fish samples, it was found that liver or skin contained about 1.5-fold the level in brain, about 4.0 fold the level in muscles and about 6.5 fold the level in gills. Immunoassay proved to be as reliable an analytical tool as gas chromatography in this case.     

Adsorption characteristics of 2,4-dichlorophenoxyacetic acid (2,4-D) from aqueous solution on powdered activated carbon

The removal of 2,4-dichlorophenoxyacetic acid (2,4-D), one of the most commonly used phenoxy acid herbicides, from aqueous solution was studied by using acid-washed powdered activated carbon (PAC) as an adsorbent in a batch system. Adsorption equilibrium, kinetics, and thermodynamics were investigated as a function of initial pH, temperature, and initial 2,4-D concentration. Powdered activated carbon exhibited the highest 2,4-D uptake capacity of 333.3 mg g(-1) at 25 degrees C and an initial pH value of 2.0. Freundlich, Langmuir, and Redlich-Peterson isotherm models were used to express the equilibrium data of 2,4-D depending on temperature. Equilibrium data fitted very well to the Freundlich equilibrium model in the studied concentration range of 2,4-D at all the temperatures studied. Three simplified models including pseudo-first-order, pseudo-second-order, and saturation-type kinetic models were used to test the adsorption kinetics. It was shown that the adsorption of 2,4-D on PAC at 25, 35, and 45 degrees C could be best fitted by the saturation-type kinetic model with film and intraparticle diffusions being the essential rate-controlling steps. The activation energy of adsorption (EA) was determined as--1.69 kJ mole(-1). Using the thermodynamic equilibrium coefficients obtained at different temperatures, the thermodynamic constants of adsorption (deltaG degrees, deltaH degrees, and deltaS degrees) were also evaluated.     

Effects of environmental biomass-producing factors on Cd uptake in two Swedish ecotypes of Pinus sylvestris

A factorial design was used to study direct effects of external biomass-producing factors such as light, temperature and photoperiod on cadmium (Cd) uptake and indirect effects, via change in biomass production in two ecotypes of Scots pine (Pinus silvestris). The aim was to find out if the external factors affect the Cd uptake directly or via change in biomass production, and if the effect differs between ecotypes. Seedlings were grown under 10 combinations of external factors, i.e. temperature (15 and 20 degrees C), light intensity (50 and 200 micromol photons m(-2) S(-1)), photoperiod (18 h light/8 h darkness and continuous light) and external Cd concentration (totally 1.88 and 7.50 micromol). The treatment lasted for 18 days and Cd concentrations in roots and shoots were determined by AAS. The results showed that an increased biomass production increased the total Cd uptake but had a dilution effect on the Cd concentration, especially in the root tissues. The external factors tested did not have any direct effects on the Cd untake, only in the case of Cd translocation to the shoot did the higher temperature show a direct increase, but only in the southern ecotype. The two ecotypes reacted differently in Cd uptake and translocation to the external factors studied. The relative Cd uptake creased with increasing photoperiod in the northern but not in the southern ecotype. The southern ecotype decreased the Cd concentration in the shoot with increased light intensity caused by a dilution effect due to extensive shoot growth of this ecotype. The conclusion is that the uptake in pine seedlings is mainly regulated via biomass production, and not directly by light and temperature and that resulting plant Cd contents to a certain extent depend on plant origin.     

Sorption of pentachlorophenol on pine bark

The minimization of pentachlorophenol (PCP) transport in the environment driven by industrial wastewater discharges can be accomplished by sorption in natural, available and low cost by-products like pine bark. Taking into account that PCP is a chemical which behaviour is highly dominated by the surrounding features, this work intended to evaluate the sorption kinetics and equilibrium parameters according to the pH and temperature as well as the pine bark particle size. The PCP uptake by pine bark showed to be faster in the initial phase followed by a slower process, being 24 h the suitably time to reach the sorption equilibrium in the range of pH studied. The neutral PCP species showed to have higher binding capacity to pine bark than the anionic PCP, which was reflected in a decrease in the distribution coefficient (Kd) of the linear sorption isotherm with the increase of solution pH from 2 to 7. On the other hand, between 10 degrees C and 35 degrees C, the temperature does not seem to play a significant role in the PCP sorption by pine bark, while the sorbent size is a key parameter to enhance the overall process.     

Uptake of dieldrin, dimethoate and permethrin by cyanobacteria, Anabaena sp. and Aulosira fertilissima

Blue-green algae showed a poor ability to pick up and concentrate dieldrin and dimethoate. However, the uptake and bioconcentration factor for permethrin was very high. The uptake of dieldrin by Anabaena and Aulosira ranged from 5.1 to 73.2 and 5.5 to 17.4 microg g(-1) (ppm), respectively. The uptake of permethrin was from 9.0 to 249.7 and 4.6 to 1422.5 microg g(-1) by Anabaena and Aulosira, respectively. The highest bioconcentration factors for permethrin in Anabaena and Aulosira were 813 and 2373, respectively. This was followed by the bioconcentration factor of dieldrin (620) and dimethoate (119) in Aulosira fertilissima.     

Influence of particle characteristics and organic matter content on the bioavailability and bioaccumulation of pyrene by clams

Hydrophobic chemicals are known to associate with sediment particles including those from both suspended particulate matter and bottom deposits. The complex and variable composition of natural particles makes it very difficult therefore, to predict the bioavailability of sediment-bound contaminants. To overcome these problems we have previously devised a test system using artificial particles, with or without humic acids, for use as an experimental model of natural sediments. In the present work we have applied this experimental technique to investigate the bioavailability and bioaccumulation of pyrene by the freshwater fingernail clam Sphaerium corneum. The uptake and accumulation of pyrene in clams exposed to the chemical in the presence of a sample of natural sediment was also investigated. According to the results obtained, particle surface properties and organic matter content are the key factors for assessing the bioavailability and bioaccumulation of pyrene by clams.     

Desorption kinetics studies on PAH-contaminated soil under varying temperatures

The purpose of this study was to investigate the effect of temperature on the release of polycyclic aromatic hydrocarbons (PAHs) from aged contaminated soil. The release of fluorene, phenanthrene, anthracene, fluoranthene and pyrene at 7, 15, 18 and 23 degrees C was studied using a column leaching method with a hydraulic retention time of 0.5 h. As the temperature declined from 23 to 7 degrees C the concentrations decreased by a factor of 11-12 for all the studied compounds except for anthracene, which only decreased by a factor 7. Rate constants at maximum release rate at the four studied temperatures were assessed. From temperature dependence studies, apparent activation energies of desorption, E*(des), were calculated. E*(des)-values appeared to be in the range of 105-137 kJ mol(-1) for the studied PAHs and increased with the LeBas molar volume of the compounds. The increase of E*(des) with increased molecular size indicates stronger sorption with increased hydrophobicity of the compounds.     

Experimental and modeling study of the effect of CO and H2 on the urea DeNO(x) process in a 150kW laboratory reactor

An experimental and modeling investigation has been performed to study the effect of process additives, H2 and CO on NO(x) removal from flue gases by a selective non-catalytic reduction process using urea as a reducing agent. Experiments were performed with a flow reactor in which flue gas was generated by the combustion of propane in air at 3% excess oxygen and the desired levels of initial NO(x) (500ppm) were achieved by doping the flame with ammonia. Experiments were performed throughout the temperature range of interest, i.e. from 850 to 1200 degrees C for investigation of the effects of the process additives on the performance of aqueous urea DeNO(x). Subsequently, computational kinetic modeling with SENKIN code was performed to analyze the performance of urea providing a direct comparison of modeling prediction with experimental measurements. With CO addition, a downwards shift of 215 degrees C in the peak reduction temperature from 1125 to 910 degrees C was observed during the experimentation while the kinetic modeling suggests it to be 150 degrees C, i.e. from 1020 to 870 degrees C. The addition of H2 impairs the peak NO(x) reduction but suggests a low temperature application of the process. A downward shift of 250 degrees C in the peak reduction temperature, from 1020 to 770 degrees C, was observed during kinetic modeling studies. The kinetic modeling shows a good qualitative agreement with the experimental observations and reveals additional information about the process.     

Formation of chlorinated hydrocarbons from the reaction of chlorine atoms and activated carbon

The reactions of chlorine atoms and activated carbon have been studied over the temperature range of 200-400 degrees C using an isothermal flow reactor in conjunction with 337 nm laser photolysis of Cl2. These studies have shown that carbon tetrachloride is the major product, with chloroform, methylene chloride, and methyl chloride being formed in progressively decreasing yields. Trace quantities of methane, ethane, and dichloroethylenes were also observed. Mechanisms of carbon fragmentation by successive addition of chlorine atoms are proposed. The formation of small chlorinated hydrocarbons by the direct reaction of chlorine with carbon may be a key link in both the de novo and precursor pathways of formation of PCDD/F.     

Bacterial responses to temperature during aeration of pig slurry

The temperature effect on total anaerobic and aerobic bacterial growth in pig slurry was studied using low level batch aeration treatments. Five bioreactors were built using Plexiglas tubes to perform five temperature treatments (5 degrees C, 10 degrees C, 15 degrees C, 20 degrees C, and 25 degrees C). An airflow rate of 0.129 L/min/L manure was used to aerate manure contained in all reactors. Data showed that temperature had a profound impact on the aerobic counts in pig slurry during the aeration process. When the temperature increased from 15 degrees C to 25 degrees C, the average oxidation-reduction potential decreased from +40 mV to -60 mV, accompanied by a 75% reduction of aerobic bacteria in the manure. At 25 degrees C, the anaerobic counts were consistently higher than aerobic counts for most of days. A quadratic relationship was observed between the aerobic counts and the oxidation-reduction potential with a correlation coefficient of 0.8374. To reduce odor generation potential, the oxidation-reduction potential in the manure should be maintained at +35 mV or higher.     

Entrained-flow adsorption of mercury using activated carbon

Bench-scale experiments were conducted in a flow reactor to simulate entrained-flow capture of elemental mercury (Hg0) by activated carbon. Adsorption of Hg0 by several commercial activated carbons was examined at different C:Hg ratios (by weight) (350:1-29,000:1), particle sizes (4-44 microns), Hg0 concentrations (44, 86, and 124 ppb), and temperatures (23-250 degrees C). Increasing the C:Hg ratio from 2100:1 to 11,000:1 resulted in an increase in removal from 11 to 30% for particle sizes of 4-8 microns and a residence time of 6.5 sec. Mercury capture increased with a decrease in particle size. At 100 degrees C and an Hg0 concentration of 86 ppb, a 20% Hg0 reduction was obtained with 4- to 8-micron particles, compared with only a 7% reduction for 24- to 44-micron particles. Mercury uptake decreased with an increase in temperature over a range of 21-150 degrees C. Only a small amount of the Hg0 uptake capacity is being utilized (less than 1%) at such short residence times. Increasing the residence time over a range of 3.8-13 sec did not increase adsorption for a lignite-based carbon; however, increasing the time from 3.6 to 12 sec resulted in higher Hg0 removal for a bituminous-based carbon.     

Accumulation pattern and biotransformation enzyme induction in rainbow trout embryos exposed to sublethal aqueous concentrations of 3,3',4,4'-tetrachlorobiphenyl

Accumulation pattern of 3,3',4,4'-tetrachlorobiphenyl (PCB 77) and the exposure time needed to activate the monooxygenase (EROD) and conjugation (GST) enzyme systems of fish at the advanced embryonic stage were studied. Eyed stage embryos of rainbow trout (Oncorhynchus mykiss) were exposed to sublethal doses (0, 1, 10, and 100 micrograms/l) of PCB 77. Results indicated direct accumulation of the chemical into the eggs, but the exposure time was not long enough for PCB 77 to reach constant steady state. However, at the two lowest test concentrations (1 microgram/l and 10 micrograms/l) a temporary plateau at chemical accumulation was reached at the third exposure day (185 and 1221 ng PCB/g egg w.w). At the highest concentration (100 micrograms/l) the decrease in the accumulation rate was already evident after the first day (2182 ng PCB/g egg w.w). The chemical uptake increased again at day 7 in all the exposure groups. That event could have been caused by the increased metabolic rate of the embryos in preparation for the upcoming hatching event. The microsomal CYP1A monooxygenase system (EROD) was shown to be a sensitive indicator of embryonic exposure, being induced at the low (1 microgram/l, 182 ng/g egg) PCB concentration and after a short (3 day) exposure time. The conjugation enzyme system (GST) was shown to be functioning already at the advanced embryonic stage, although no response to the studied chemical stress was detected.     

Photocatalytic degradation of imazethapyr herbicide at TiO2/H2O interface

The photocatalytic degradation of imazethapyr, a herbicide of the imidazolinone family, was investigated in an aqueous suspension of titanium dioxide used as a catalyst. A pseudo-first order kinetic model was employed to discuss the results. The effect of catalyst loading, initial concentration of imazethapyr, hydrogen peroxide, pH value, and temperature were investigated. Imazethapyr disappearance as a function of irradiation time was analyzed by HPLC. The ammonium ion formation was determined spectrophotometrically at 694 nm. The degradation was observed to proceed more favorably at natural pH (ca. 4.4) when the pH was varied in the range from 2 to 11. The addition of hydrogen peroxide to the TiO2 suspension enhanced the degradation rate constant up to 5.0x10(-3) mol l-1, but decreased it at higher concentrations. The degradation rate constants decreased by 19% with a temperature increase from 20 to 40 degrees C in the TiO2 suspension, whereas a 16% increase in imazethapyr direct photolysis was observed for the same temperature range. This behavior indicates the occurrence of physisorption between TiO2 and imazethapyr molecules.     

Study on fluoride emission from soils at high temperature related to brick-making process

Characteristics of fluoride emission from 12 soils at temperatures of 400-1,100 degrees C related to the brick-making process were studied. The results obtained in this study indicate that fluoride emission as gaseous HF and SiF4 was related to the firing temperature, soil total fluoride content, soil composition and calcium compounds added to soils. Soils began to release fluoride at temperatures between 500 and 700 degrees C. Marked increases of the average fluoride mission rate from 57.2% to 85.4% of soil total fluoride were noticed as the heating temperature was increased from 700 to 1,100 degrees C. It was found that the major proportion (over 50%) of the soil total fluoride was emitted from soils at approximate 800 degrees C. The amount of fluoride released into the atmosphere when heated depended on the total fluoride contents in the soils. Correlation analysis showed that the soil composition, such as cation exchange capacity, exchangeable calcium and CaCO3, had some influence on fluoride emission below 900 degrees C, but had no influence at temperatures above 900 degrees C. Addition of four calcium compounds (CaO, CaCO3, Ca(OH)2, and CaSO4) at 1.5% by weight raised the temperature at which fluoride began to be released to 700 degrees C. The greatest decrease in fluoride emission among the four calcium compound treatments was found with CaCO3.     

A kinetic study on oxidation of pentachlorophenol by ozone

The kinetics of pentachlorophenol (PCP) ozonation in terms of the gaseous O3 and dissolved PCP concentrations has been investigated. When the O3 concentration in the gas phase was in the range of 10 to 40 g O3/m3, the O3 dissolved for a short time period was proportional to the gaseous O3 concentration. In this range, the ozonation reaction was first order for each reactant and the overall reaction was second order. At 25 degrees C, in an aqueous solution, the reaction rate constant was estimated to be 10.048 L/mol.sec. The reaction rate was much greater than the mass-transfer rate, indicating that the reaction of O3 and PCP was an interface reaction on the surface of gaseous O3 bubbles. The final product of the PCP ozonation was oxalic acid, with the carbon yield of the reaction being 59.4%. The ozonation of PCP in the aqueous solution was not a radical reaction but a direct reaction between O3 and PCP molecules under the conditions investigated in this study, since O3 has a high selectivity toward PCP. The reaction rate increased with the reaction temperature up to 35 degrees C but decreased at temperatures greater than 35 degrees C due to the decreased solubility of O3. The addition of H2O2 did not increase the reaction rate significantly.     

Corrected first-order model of DEHP degradation

Corrected first-order model was applied to describe the biological removal of di-(2-ethylhexyl) phthalate (DEHP) in sludge-amended soil along with batch and continuous-flow anaerobic reactors with different initial/influent DEHP concentrations and hydraulic retention times. Only two kinetic parameters - the first-order rate coefficient k describing the overall kinetics of the process and the coefficient alpha characterizing the fraction of non-degradable DEHP - were used to fit the array of experimental data published earlier. The values of k and alpha estimated for DEHP removal from different sludges at 35 degrees C varied within the range of 0.03-0.07 d(-1) and 0.25-0.5, respectively. In sludge-amended soil, the first-order kinetic coefficient k increased from 0.007 to 0.028 d(-1) and the fraction of non-degradable DEHP alpha decreased from 0.6 to 0.5 with the increase in incubation temperature from 5 to 20 degrees C. The rate coefficient k increased by a factor of 2 when the temperature increased from 5 to 10 degrees C or from 10 to 20 degrees C.     

Effect of UV radiation and temperature on mineralization and volatilization of coumaphos in water

This study was undertaken to determine the dissipation and degradation of coumaphos [O-(3-chloro-4-methyl-2-oxo-2H-1-benzopyran-7-yl) O,O-diethyl phosphorothioate] under different sunlight conditions and at different temperatures. The effect of the ultra violet (UV) component of solar radiation was also studied using quartz tubes in addition to other radiation in the visible range using glass tubes and the results were compared with those obtained under the dark light conditions. Water suspensions of coumaphos were incubated at three temperatures viz. 22 degrees C, 37 degrees C and 53 degrees C in closed systems to study the effect of temperature. Volatilization, mineralization and degradation of coumaphos increased with an increase in temperature and exposure to solar radiation, particularly under the UV component of the solar radiation. Major loss of the pesticide occurred through volatilization. The optimum temperature for the degradation of coumaphos was found to be at 37 degrees C. The data obtained from the mineralization and degradation studies indicated that 53 degrees C crosses the biological range for suitable growth of microorganism. UV radiation exposure along with maintaining temperature at 37 degrees C may prove useful in the dissipation and/or degradation of coumaphos prior to its disposal as waste from cattle dipping vats.