Principles of microbial PAH-degradation in soil

Interest in the biodegradation mechanisms and environmental fate of polycyclic aromatic hydrocarbons (PAHs) is motivated by their ubiquitous distribution, their low bioavailability and high persistence in soil, and their potentially deleterious effect on human health. Due to high hydrophobicity and solid-water distribution ratios, PAHs tend to interact with non-aqueous phases and soil organic matter and, as a consequence, become potentially unavailable for microbial degradation since bacteria are known to degrade chemicals only when they are dissolved in water. As the aqueous solubility of PAHs decreases almost logarithmically with increasing molecular mass, high-molecular weight PAHs ranging in size from five to seven rings are of special environmental concern. Whereas several reviews have focussed on metabolic and ecological aspects of PAH degradation, this review discusses the microbial PAH-degradation with special emphasis on both biological and physico-chemical factors influencing the biodegradation of poorly available PAHs.     

Effects of freezing on the survival of Escherichia coli and Bacillus and response to UV and chlorine after freezing.

Escherichia coli (E. coli) and Bacillus megaterium bacteria were frozen at -15 degrees C using a freezer and a spray freezing method. The frozen Bacillus spores were also exposed to UV and free chlorine. An average of 4.7-log inactivation was obtained from the spray ice with 2-day storage time, while the freezer freezing only caused 0.84-log reduction with the same storage time. Significantly higher inactivation levels were observed for the E. coli cells with 2-day storage compared with those without storage. The spray freezing was found more effective in killing the E. coli cells, while more cells were sublethally injured by the freezer freezing. Freezing did not kill the Bacillus megaterium spores, but affected their response to UV and chlorine. Greater inactivation levels were observed at higher free chlorine doses or longer contact time, and the UV fluence-response curve showed initial rapid kill followed by tailing for the frozen spores.     

Effects of butachlor on microbial populations and enzyme activities in paddy soil

This paper reports the influences of the herbicide butachlor (n-butoxymethlchloro -2', 6'-diethylacetnilide) on microbial populations, respiration, nitrogen fixation and nitrification, and on the activities of dehydrogenase and hydrogen peroxidase in paddy soil. The results showed that the number of actinomycetes declined significantly after the application of butachlor at different concentrations ranging from 5.5 microg g(-1) to 22.0 microg g(-1) dried soil, while that of bacteria and fungi increased. Fungi were easily affected by butachlor compared to the bacteria. The growth of fungi was retarded by butachlor at higher concentrations. Butachlor however, stimulated the growth of anaerobic hydrolytic fermentative bacteria, sulfate-reducing bacteria (SRB) and denitrifying bacteria. The increased concentration of butachlor applied resulted in the higher number of SRB. Butachlor inhibited the growth of hydrogen-producing acetogenic bacteria. The effect of butachlor varied on methane-producing bacteria (MPB) at different concentrations. Butachlor at the concentration of 1.0 microg g(-1) dried soil or less than this concentration accelerated the growth of MPB, while at 22.0 microg g(-1) dried soil showed an inhibition. Butachlor enhanced the activity of dehydrogenase at increasing concentrations. The soil dehydrogenase showed the highest activity on the 16th day after application of 22.0 microg g(-1) dried soil of butachlor. The hydrogen peroxidase could be stimulated by butachlor. The soil respiration was depressed during the period from several days to more than 20 days, depending on concentrations of butachlor applied. Both the nitrogen fixation and nitrification were stimulated in the beginning but reduced greatly afterwards in paddy soil.     

Fate of parathion in artificially fortified grape juice processed into wine

"Semellon" grape juice fortified with a high level of 25 ppm parathion was fermented using Saccharomyces cerevisiae var. ellipsoideus. After 12 days inte parathion levels in the wine and lees were 10.3 and 156 ppm, respectively; the paraoxon, aminoparathion, and p-nitrophenol levels in the wine were 0.16, 0.20, and 4.5 ppm, respectively, and in the lees were 0.04, 3.1 and 10 ppm, respectively. Thus, hydrolysis of parathion to p-nitrophenol and parathion sorption to sedimented particulate matter were important pathways for parathion residue reduction in the wine. The 56-day-old finished wine just prior to bottling contained 8.8 ppm parathion, 0.04 ppm paraoxon, 0.21 ppm aminoparathion, and 3.0 ppm p-nitrophenol. Two months storage at 24 degrees, 12 degrees, 4 degrees, and -20 degrees C had no effect on paraoxon and aminoparathion residue levels in the wine; parathion residues in wine decreased at all storage temperatures.     

Photocatalytic degradation of azo dyes by nitrogen-doped TiO2 nanocatalysts

This study examined the photocatalytic degradation of three azo dyes, acid orange 7 (AO7), procion red MX-5B (MX-5B) and reactive black 5 (RB5) using a new type of nitrogen-doped TiO2 nanocrystals. These newly developed doped titania nanocatalysts demonstrated high reactivity under visible light (lambda>390 nm), allowing more efficient usage of solar light. The doped titania were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Experiments were conducted to compare the photocatalytic activities of nitrogen-doped TiO2 nanocatalysts and commercially available Degussa P25 powder using both UV illumination and solar light. It is shown that nitrogen-doped TiO2 after calcination had the highest photocatalytic activity among all three catalysts tested, with 95% of AO7 decolorized in 1 h under UV illumination. The doped TiO2 also exhibited substantial photocatalytic activity under direct sunlight irradiation, with 70% of the dye color removed in 1h and complete decolorization within 3 h. Degussa P25 did not cause detectable dye decolorization under identical experimental conditions using solar light. The decrease of total organic carbon (TOC) and evolution of inorganic sulfate (SO4(2-)) ions in dye solutions were measured to monitor the dye mineralization process.     

Heavy metal pollution and forest health in the Ukrainian Carpathians

The Ukrainian Carpathians are characterized by high air pollution caused by emissions from numerous industries. We have been monitoring the state of forests in this region since 1989. The highest levels of tree defoliation (>30%) are found close to industrial emission sources and in the upper mountain forests of the Ivano-Frankivsk and Chernivtsi regions. This is caused by a combination of strong anthropogenic influences (pollution, illegal uses, recreation) as well as poor site and climatic conditions. In the Ivano-Frankivsk region, Cd and Mo accumulate in forest soils; Cr, Mo and Zn soil concentrations are higher than their limit levels; and Pb concentrations exceed toxic levels close to industrial areas (10% of the region territory). Local background levels of heavy metals are greatly exceeded in snow close to industrial regions. Analysis of correlation matrices shows that the chemical elements Ba, Cd, Co, Cr, Cu, Mo, Ni, Pb, V and Zn occur at pollution levels in natural ecosystems in the Ukrainian Carpathians. Maximum concentrations of toxic elements occur in the oak forest zone; the most industrially developed area of the region. Toxic heavy metals in the Ukrainian Carpathians forests enter with precipitation and dustfall, then become fixed in soil and accumulate in leaves, needles of vascular plants and mosses. Concentrations of these metals decrease with altitude: highest in the oak forests, less in beech, and lowest in the spruce forest zones. However, some chemical elements have the highest concentrations in spruce forests; V in needles, As in snow, and Ba and Al in soils.     

Relevance of coplanar PCBs for TEQ emission of fluidized bed incineration and impact of emission control devices

Five fluidized bed incinerators combusting municipal solid waste were assessed for the impact of coplanar PCBs on total TEQ emission. In 17 stack measurements, the coplanar PCBs contributed on average less than 3% to total TEQ with a maximum contribution of 7.5% to total TEQ in one measurement. Differences in the design of the flue gas cooling section did not show an effect on the impact of coplanar PCBs on total TEQ. The effect of emission control devices on the impact of coplanar PCBs on the total TEQ was studied in more detail at one incinerator. The relative contribution of PCBs to total TEQ increased along the flue gas line. This was caused by a slightly higher removal efficiency for TEQ relevant PCDDs/PCDFs compared to coplanar PCBs by the bag filters and a higher destruction efficiency for PCDDs/PCDFs compared to PCBs by the SCR catalyst. Additionally, the removal efficiencies of the emission control devices (bag filters and catalyst) for other chlorinated aromatic compounds which have been proposed as TEQ indicator compounds (polychlorinated benzenes and polychlorinated phenols) were compared with those for PCDDs/PCDFs and coplanar PCBs. Removal efficiencies for polychlorinated benzenes or polychlorinated phenols considerably differed from those of PCDD/PCDF and coplanar PCBs. Implications for TEQ assessments using indicator compounds as proposed in the literature are discussed.     

Preparations of organobentonite using nonionic surfactants

Due to hydrophilic environment at its surface, natural bentonite is an ineffective sorbent for nonpolar nonionic organic compounds in water even though it has high surface area. The surface properties of natural bentonite can be greatly modified by simple ion-exchange reactions with large organic cations (cationic surfactants) and this organobentonite is highly effective in removing nonionic organic compounds from water. Cationic surfactant derived organobentonites have been investigated extensively for a wide variety of environmental applications. In this study, the preparation of organobentonite using nonionic surfactants has been investigated for the first time. Results indicate that nonionic surfactants intercalates into the interlamellar space of bentonite and may demonstrate higher sorption capacity than cationic surfactant. It is possible to create large interlayer spacing and high organic carbon content organobentonite by use of nonionic surfactants with suitable balance between the hydrocarbon and ethylene oxide chain lengths. In addition, nonionic surfactant derived organobentonites are more chemically stable than cationic surfactant derived organobentonites.     

Correlation of gas chromatographic properties of chlorobenzenes and polychlorinated biphenyls with the occurrence of reductive dechlorination by untamed microorganisms

To understand the dechlorination ability of chlorobenzenes (CBs) and polychlorinated biphenyls (PCBs) by untamed microorganisms under anaerobic condition and to correlate gas chromatographic properties with the occurrence of reductive dechlorination, introduction of CBs and PCBs in the culture medium inoculated with microorganisms from sludge and sediment, respectively, were performed. Three kinds of culture media preparing from sludge, river water and a synthetic medium were used in the experiments. HCB was degraded to 1,3,5-trichlorobenzene (1,3,5-TCB) and 1,3-dichlorobenzene (1,3-DCB) in both sludge medium and synthetic medium with inoculated microorganisms. Three PCB congeners including 2,3,4-, 3,4,5- and 2,3,4,5-CBp (chlorinated biphenyl) were not found to be dechlorinated in the river water medium with inoculation culture but to be dechlorinated in the synthetic medium. MNDO methodology was used to compute theoretical dechlorination reaction heats and GC-ECD techniques were used to estimate chromatographic data of CB and PCB congeners. Both CB and PCB congeners showed that dechlorination by untamed microorganisms under anaerobic mixed cultures were more likely to occur when larger amounts of energy were released and greater deltaln RRT value between the parent congener and the daughter product was observed. Deltaln RRT provided a more precise information on the singularity of PCBs ortho-dechlorination in an aspect of thermodynamic favorable rule.     

Identification of the dimethylbenzyl mercapturic acid in urine of rats administered with 1,2,4-trimethylbenzene

A study was undertaken of the mercapturic acid metabolism of 1,2,4-trimethylbenzene in the rat. Of three regioisomeric dimethylbenzyl mercapturic acids, i.e. 2,4-, 2,5- and 3,4-dimethylbenzyl isomers, the third isomer was not found in the urinary mercapturic acid isolated by preparative HPLC, from the comparison of NMR spectrum of the isolate with those of authentic specimens. The urinary mercapturate was then assigned to 2,4- and/or 2,5-dimethylbenzyl isomers. The excretion rate of the mercapturic acid was 14-20% of dose as 2,4-dimethylbenzyl isomer.