RESUMO

Shifts in the bacterial-community dynamics, bioavailability, and biodegradation of polycyclic aromatic hydrocarbons (PAHs) of chronically contaminated soil were analyzed in Triton X-100-treated microcosms at the critical micelle concentration (T-CMC) and at two sub-CMC doses. Only the sub-CMC-dose microcosms reached sorbed-PAH concentrations significantly lower than the control: 166±32 and 135±4mgkg-1 dry soil versus 266±51mgkg-1; consequently an increase in high- and low-molecular-weight PAHs biodegradation was observed. After 63days of incubation pyrosequencing data evidenced differences in diversity and composition between the surfactant-modified microcosms and the control, with those with sub-CMC doses containing a predominance of the orders Sphingomonadales, Acidobacteriales, and Gemmatimonadales (groups of known PAHs-degrading capability). The T-CMC microcosm exhibited a lower richness and diversity index with a marked predominance of the order Xanthomonadales, mainly represented by the Stenotrophomonas genus, a PAHs- and Triton X-100-degrading bacterium. In the T-CMC microcosm, whereas the initial surface tension was 35mNm-1, after 63days of incubation an increase up to 40mNm-1 was registered. The previous observation and the gas-chromatography data indicated that the surfactant may have been degraded at the CMC by a highly selective bacterial community with a consequent negative impact on PAHs biodegradation. This work obtained strong evidence for the involvement of physicochemical and biologic influences determining the different behaviors of the studied microcosms. The results reported here contribute significantly to an optimization of, surfactant-enhanced bioremediation strategies for chronically contaminated soil since the application of doses below the CMC would reduce the overall costs.

RESUMO

Polycyclic aromatic hydrocarbons (PAH) are neutral, nonpolar and hydrophobic molecules that tend to sorb onto soil organic matter. Chemical oxidation is a good choice to avoid the limitations of bioremediation. To evaluate the efficiency of different types of oxidation (permanganate, hydrogen peroxide, and persulfate) and activation (heat, alkaline, and iron), batch reactors were prepared. The soil was contaminated with phenanthrene and pyrene (1200 ± 200 and 2800 ± 100mg per kg of dry soil, respectively) and aged for fifteen months. Treatments were prepared with 10g of contaminated dry soil and 20ml of water and incubated at room temperature for 7 days. Analyses of phenanthrene and pyrene concentrations, soil pH and electric conductivity were performed. Counts of heterotrophic cultivable bacteria on R2A medium and PAH-degraders were carried out after 7 days of treatment. The persulfate treatment at room temperature, without the addition of activators, achieved better results than treatments with the same doses of permanganate or hydrogen peroxide. All the strategies to improve persulfate treatments yielded higher degradation of pyrene than the biological control, as expected from the structural description of this compound by Clar's model. The thermal activation of persulfate (65°C for 6h) led to the degradation of more than 90% of both PAHs after 7 days of treatment.

Assuntos

RESUMO

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous compounds with carcinogenic and/or mutagenic potential. To address the limitations of individual remediation techniques and to achieve better PAH removal efficiencies, the combination of chemical and biological treatments can be used. The degradation of phenanthrene (chosen as a model of PAH) by persulfate in freshly contaminated soil microcosms was studied to assess its impact on the biodegradation process and on soil properties. Soil microcosms contaminated with 140 mg/kgDRY SOIL of phenanthrene were treated with different persulfate (PS) concentrations 0.86-41.7 g/kgDRY SOIL and incubated for 28 days. Analyses of phenanthrene and persulfate concentrations and soil pH were performed. Cultivable heterotrophic bacterial count was carried out after 28 days of treatment. Genetic diversity analysis of the soil microcosm bacterial community was performed by PCR amplification of bacterial 16S rDNA fragments followed by denaturing gradient gel electrophoresis (DGGE). The addition of PS in low concentrations could be an interesting biostimulatory strategy that managed to shorten the lag phase of the phenanthrene biological elimination, without negative effects on the physicochemical and biological soil properties, improving the remediation treatment.

Assuntos

RESUMO

The ability of thermal activated peroxydisulfate (PS) of mineralizing phenol at 70°C from contaminated waters is investigated. Phenol in concentrations of 10(-4) to 5×10(-4)M is quantitatively depleted by 5×10(-3) to 10(-2)M activated PS in 15 min of reaction. However, mineralization of the organic carbon is not observed. Instead, an insoluble phenol polymer-type product is formed. A reaction mechanism including the formation of phenoxyl radicals and validated by computer simulations is proposed. High molecular weight phenolic products are formed by phenoxyl radical H-abstraction reactions. This is not the case for the room temperature degradation of phenol by sulfate radicals where sulfate addition to the aromatic ring mainly leads to the generation of hydroxycyclohexadienyl radicals leading to hydroxybenzenes and oxidized open chain products. Therefore, a change in the reaction mechanism is observed with increasing temperature, and thermal activation of PS at 70°C does not lead to the mineralization of phenol. Thus PS activation at 70°C may be considered a potential method to reduce the load of phenol in polluted waters by polymerization.

Assuntos

RESUMO

The kinetics and mechanism of the thermal activation of peroxydisulfate, in the temperature range from 60 to 80 degrees C, was investigated in the presence and absence of sodium formate as an additive to turn the oxidizing capacity of the reaction mixture into a reductive one. Trichloroacetic acid, TCA, whose degradation by a reductive mechanism is well reported in the literature, was used as a probe. The chemistry of thermally activated peroxydisulfate is described by a reaction scheme involving free radical generation. The proposed mechanism is evaluated by a computer simulation of the concentration profiles obtained under different experimental conditions. In the presence of formate, SO(4)(-) radicals yield CO(2)(-), which are the main species available for degrading TCA. Under the latter conditions, TCA is more efficiently depleted than in the absence of formate, but otherwise identical conditions of temperature and [S(2)O(8)(2-)]. We therefore conclude that activated peroxydisulfate in the presence of formate as an additive is a convenient method for the mineralization of substrates that are refractory to oxidation, such as perchlorinated hydrocarbons and TCA. This method has the advantage that leaves no toxic residues.

Assuntos