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Detection and identification of substituted phenols as intermediates of concurrent bacterial degradation of the phenoxy herbicides MCPP and 2,4-D.

The concurrent bacterial degradation of 2-(2-methyl-4-chlorophenoxy)propionic acid and 2,4-dichlorophenoxyacetic acid was studied using a stirred tank reactor and a bacterial culture which had been originally derived by enrichment with MCPP. High pressure liquid chromatographic methodology was used to measure both herbicides and it also resolved the corresponding phenols as intermediates, i.e., 2-methyl-4-chlorophenol and 2,4-dichlorophenol. Gas chromatography-mass spectrometry was used to verify the intermediates. UV scans of spent cultures showed that the wave-length of maximum absorption shifted from 282 nm to 280 nm toward the end of incubation, but the characteristic peaks of maximum absorption of these compounds could not be used resolved because of the overlap.

2,4-Dichlorophenoxyacetic Acid↗

Application of electrochemically prepared polypyrrole-polyvinyl sulphonate films to DNA biosensor.

Double stranded calf thymus deoxyribonucleic acid (DNA) was physisorbed onto polypyrrole-polyvinyl sulphonate (PPY-PVS) films electrochemically deposited onto indium-tin-oxide (ITO) coated glass plates. These DNA immobilized PPY-PVS films optimized for various conditions, such as polymerization potential, pH of buffer, DNA concentration and scan rate were characterized using Fourier-transform infrared (FT-IR) spectroscopy, atomic force microscopy (AFM) and cyclic voltammetry (CV) techniques, respectively. The amperometric response studies of these DNA/PPY-PVS electrodes were carried out as a function of 2-aminoantharcene (2-AA, 0.01-20 ppm) and o-chlorophenol (OCP, 0.1-30 ppm) concentration, respectively at 25 degrees C. The observed amperometric current arising due to oxidation of guanine in the DNA/PPY-PVS films decreased linearly with the increase in the concentration of 2-AA and OCP. It has been revealed that 10 ppm of 2-AA is sufficient to reduce the observed guanine oxidation peak current by approximately -95+/-10% as compared to the reported values. A 25 ppm of OCP was capable enough to reduce the guanine oxidation current to zero. These DNA/PPY-PVS electrodes were found to have a shelf life of about 4 months when stored at 25 degrees C.

Anthracenes↗

Inhibition of PCDD/Fs formation from dioxin precursors by calcium oxide.

Research aimed at understanding the inhibition effect of CaO on polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) formation form dioxins precursors, such as chlorophenols (CPs) and chlorobenzenes (CBs). The results indicated that a clear dioxin inhibition effect occurred both in open and sealed system when CaO was used. In the open system, PCDDs were the main congeners and the inhibition efficiency was all over 99% in the experiments. In the experiments with CaO, less than 0.1% of the initial PCP was detected in the absorption tube and only about 1% of the initial PCP was examined as calcium pentachlorophenate in the reaction tube. In the sealed system, the inhibition efficiency was over 90% at temperature range between 280 and 450 degrees C when PCP was used as model precursor. When HCB and 2,3,4,5-T4CP replaced PCP, significant inhibition effect was also observed. As CaO has the advantageous properties of non-toxicity and non-volatile nature, it is our hope that the result will contribute to the development of a new technique to cope with the problem of dioxin pollution in MWIs.

Air Pollution↗

Impacts of COD and DCP loading rates on biological treatment of 2,4-dichlorophenol (DCP) containing wastewater in a perforated tubes biofilm reactor.

Biofilm processes offer considerable advantages for biological treatment of chlorophenol containing wastewaters since such industrial effluents are difficult to treat by conventional activated sludge processes. A rotating perforated tubes biofilm reactor (RTBR) was developed and used for treatment of 2,4-dichlorophenol (DCP) containing synthetic wastewater. Effects of COD and DCP loading rates on COD, DCP and toxicity removals were investigated. Percent COD removal decreased and effluent COD increased with increasing COD and DCP loading rates due to toxic effects of high DCP content in the feed. DCP and toxicity removals showed similar trends. As the DCP loading rate increased the effluent DCP content increased yielding high toxicity levels in the effluent. COD and DCP loading rates should be below 90gCODm(-2)d(-1) and 2.8gDCPm(-2)d(-1) in order to obtain more than 90% DCP and toxicity removals. However, DCP loading rates lower than 1gDCPm(-2)d(-1) are required to obtain more than 90% COD removal. Empirical equations were developed to estimate percent COD, DCP and toxicity removals as functions of COD and DCP loading rates. The coefficients of the empirical equations were determined by using the experimental data. Empirical model predictions for percent COD, DCP and toxicity removals were in good agreement with the experimental data.

Biofilms↗

Levels of chlorinated compounds (CPs, PCPPs, PCDEs, PCDFs and PCDDs) in soils at contaminated sawmill sites in Sweden.

Soil samples from five contaminated sawmill sites in Sweden were characterized with respect to chlorophenols (CP), chlorinated phenoxy phenols (PCPP, hydroxylated chlorinated diphenyl ethers), chlorinated diphenyl ethers (PCDE), chlorinated dibenzofurans (PCDF) and chlorinated dibenzo-p-dioxins (PCDD). The composition of chlorinated compounds in the soil samples was compared to the composition of two preservatives commonly used in the Scandinavian wood impregnation industry: the 2,3,4,6-tetrachlorophenol preservative called Ky-5 and the pentachlorophenol preservative Dowicide G. The levels of CPs in the soil samples ranged from 0.1 to 4500 mgkg-1 d.w., PCPPs from <0.15 to 940 mgkg-1 d.w., PCDEs from <38 to 6800 microgkg-1 d.w., PCDFs from 7.4 to 18000 microgkg-1 d.w. and PCDDs from 9.9 to 35000 microgkg-1 d.w. The resulting WHO-TEQ of PCDD/Fs in the soil samples ranged from 0.14 to 3000 microgkg-1 d.w. Despite a wide range of concentrations the congener compositions were similar within tetrachlorophenate and pentachlorophenate contaminated soils respectively. The contamination at each sawmill site may be linked to the use of either a tetrachlorphenol preservative, e.g. Ky-5, or a pentachlorophenol preservative, e.g. Dowicide G. Best-fit calculations were used to compare the chlorinated phenol contents of the preservatives to those of the soil samples. This revealed a positive correlation between the hydrophobicity (logKow) of contaminants and the ratio of their levels in soil to preservatives. The relative abundance of the chlorinated compounds varied greatly between the five sites studied, suggesting that their transport parameters differ substantially.

Benzofurans↗

POPs and organic polysufides in sediments of Lake Ladoga.

The study included one station close to a pollution source (depth 59 m) and another far from polluted areas (depth 40 m). Samples were analysed for organic chlorine, bromine and sulfur compounds. Samples taken with a corer were sliced to the layers of 0-1, 1-4, 4-7 cm etc. down to the depth of 34 cm. The dating was made with two independent methods, the 210Po method and with the soot particle counting method. The analyses were made with a multiresidue method. Gas chromatography was connected to low resolution mass spectrometry (LRMS) or to high resolution mass spectrometry (HRMS). A different extraction was applied to screen the possible occurrence of polysulfides. Typical chlorophenol and chlorohydrocarbon traces from chlorobleaching of pulp were non-detectable. Also PCDDs, PCDFs, PCBs and various organochloride pesticides, fire retardant residues PBDEs, PBDDs and PBDFs and polychlorinated phenyl salicylates were not detected. Instead, methylated dibenzothiophenes Me-DBTs and Di-Me-DBTs, typical traces of oil based defoamers used in e.g. paper mills were found in the surface layers of the polluted site. Polysulfides were analyzed from layers representing years 1955-1970 from the polluted site. The structures of five congeners were according to GC/MS dimethyl trisulfide, 1,2,3,4-tetrathiepane, pentathiane, 1,2,3,4-tetrathiane and 1,2,4,5-tetrathiepane. Many of the analyzed pollutants have not been reported earlier from Lake Ladoga. The only positive observations were from oil-based defoamers used in paper mills, and from polysulfides, which are either of natural origin or indicate a discharge in the 1950s and 1960s. Owing to the large spreadout and dilution, the concentrations are low even at moderate distances from the pollution centers.

Chlorophenols↗

Adsorption behavior of 2,4-dichlorophenol and pentachlorophenol in an allophanic soil.

The adsorption of 2,4-dichlorophenol (2,4-DCP) and pentachlorophenol (PCP) by a variable-charge soil from southern Chile was studied in a series of batch equilibration experiments. 2,4-DCP and PCP adsorption behavior was evaluated as a function of pH (pH values of 4.5, 6.0 and 7.5) in a 0.1M KCl (25 degrees C) background solution for soil material collected at three different depths (0-20 cm, 20-40 cm, and 40-60 cm). 2,4-DCP and PCP adsorption decreased with increasing soil pH, suggesting that the undissociated species were adsorbed more readily and that electrostatic repulsion may inhibit partitioning as pH increases. The PCP adsorption was greater than observed for 2,4-DCP and decreased with soil depth. Multiple regression analysis between K(d) and various soil properties indicated that the soil organic carbon content is a strong indicator of chlorophenol adsorption, and in addition to organic carbon, the soil pH is an important property controlling adsorption behavior.

Adsorption↗

Sequestration of a fluorinated analog of 2,4-dichlorophenol and metabolic products by L. minor as evidenced by 19F NMR.

Fate of halogenated phenols in plants was investigated using nuclear magnetic resonance (NMR) to identify and quantify contaminants and their metabolites. Metabolites of 4-chloro-2-fluorophenol (4-Cl-2-FP), as well as the parent compound, were detected in acetonitrile extracts using 19F NMR after various exposure periods. Several fluorinated metabolites with chemical shifts approximately 3.5 ppm from the parent compound were present in plant extracts. Metabolites isolated in extracts were tentatively identified as fluorinated-chlorophenol conjugates through examination of signal-splitting patterns and relative chemical shifts. Signal intensity was used to quantify contaminant and metabolite accumulation within plant tissues. The quantity of 4-Cl-2-F metabolites increased with time and mass balance closures of 90-110% were achieved. In addition, solid phase 19F NMR was used to identify 4-Cl-2-FP which was chemically bound to plant material. This work used 19F NMR for developing a time series description of contaminant accumulation and transformation in aquatic plant systems.

Acetonitriles↗

Flow microcalorimetric studies of phenol and its chlorinated derivatives and a theoretical evaluation of their possible inhibition mode on Chromobacterium violaceum respiration.

The general belief that chemical structure determines the biological effect of drugs has led to several techniques to establish structure-activity relationships (SAR) that is useful in the development of more active compounds. Predicting toxic effects based on SAR, one can obtain toxicological data with a low cost-benefit ratio. Chlorophenols that represent a class of toxic agents frequently used in industrial processes are not satisfactorily described in the literature in relation to their toxicity. The main objective of this work is to relate the microbial activities of phenol, anisole and their chlorinated derivatives on Chromobacterium violaceum respiration with their physicochemical properties. Anisole and its chlorinated derivatives were used to evaluate the influence of phenol acidity on biological activity. The calculations were carried out at the semi-empirical AM1 and ab initio DFT levels employing the basis sets CEP-31G, CEP-31+Ge CEP-31G** that were parameterized using the continuum-solvation model COSMO for solvent contribution. Both empirical and theoretical properties were evaluated by chemometric analyses (hierarchical cluster analysis (HCA) and principal component analysis (PCA)), to correlate the physicochemical properties of the phenol, anisole and their chlorinated derivatives with their biological activities. The results obtained for the current work indicate that the biological activities of these compounds increase as the n-octanol/water (logP) partition coefficients, ionization energies (IP), melting points (mp) and dissociation constants increase and the solvent effects (SE), enthalpies of formation (DeltafH degrees ) and proton affinities (PA) decrease.

Anisoles↗

Biodegradation kinetics of 2,4-dichlorophenol by acclimated mixed cultures.

The biodegradation kinetics of 2,4-dichlorophenol (2,4-DCP) by culture (Culture M) acclimated to mixture of 4-chlorophenol (4-CP) and 2,4-DCP and the culture (Culture 4) acclimated to 4-CP only were investigated in aerobic batch reactors. Also, pure strains isolated from mixed cultures were searched for their ability towards the biodegradation of 2,4-DCP. Culture 4 was able to completely degrade 2,4-DCP up to 80 mg/L within 30 h and removal efficiency dropped to 21% upon increasing initial concentration to 108.8 mg/L. When the Culture M was used, complete degradation of 2,4-DCP in the range of 12.5-104.4 mg/L was attained. A linear relationship between time required for complete degradation and initial 2,4-DCP concentrations was observed for both mixed cultures. It was observed that the Haldane equation can be used to predict specific degradation rate (SDR) (R(2)>0.99) as a function of initial 2,4-DCP concentrations and it adequately describes 2,4-DCP concentration profiles. Both of the mixed cultures settled well, which is important to maintain good removal efficiency for longer periods of time for real full-scale applications. Although the pure strains isolated from mixed cultures were found to have higher SDR of 2,4-DCP compared to mixed cultures, they did not settle well under quiescent conditions.

Bacteria↗

Biological treatment of synthetic wastewater containing 2,4 dichlorophenol (DCP) in an activated sludge unit.

Chlorophenol compounds present in many chemical industry wastewaters are resistant to biological degradation because of the toxic effects of such compounds on microorganisms. Synthetic wastewater containing different concentrations of 2,4 dichlorophenol (DCP) was subjected to biological treatment in an activated sludge unit. Effects of feed DCP concentration on COD, DCP, and toxicity removals and on sludge volume index were investigated at a constant sludge age of 10 days and hydraulic residence time (HRT) of 25 h. The Resazurin method based on dehydrogenase activity was used for assessment of toxicity for the feed and effluent wastewater. Percent COD, DCP, and toxicity removals decreased and the effluent COD, DCP, and toxicity levels increased with increasing feed DCP concentrations above 150 mgl(-1) because of inhibitory effects of DCP. Biomass concentration in the aeration tank decreased and the sludge volume index (SVI) increased with feed DCP concentrations above 150 mgl(-1) resulting in lower COD and DCP removal rates. The system should be operated at feed DCP concentrations of less than 150 mgl(-1) in order to obtain high COD, DCP, and toxicity removals.

Bacteria↗

The removal of phenolic compounds from aqueous solutions by organophilic bentonite.

The adsorption of p-chlorophenol (p-CP) and p-nitrophenol (p-NP) on organophilic bentonite (dodecylammonium bentonite, DDAB) was studied as a function of solution concentration and temperature. The observed adsorption rates were found to be equal to the first-order kinetics. The rate constants were calculated for temperatures ranging between 25.0-35.0 degrees C at constant concentration. The adsorption energies, E and adsorption capacity, (qm), for phenolic compounds adsorbed to organophilic bentonite were estimated by using the Dubinin-Radushkevic equation. Thermodynamic parameters from the adsorption isotherms of p-CP and p-NP on organophilic bentonite were determined. These isotherms were modeled according to Freundlich and Dubinin-Radushkevic adsorption isotherms and followed the V-shaped isotherm category with two steps. The amount of adsorption was found to be dependent on the relative energies of adsorbent-adsorbate, adsorbate-solvent and adsorbate-adsorbate interaction.

Adsorption↗

Degradation of 2,4-dichlorophenol by using glow discharge electrolysis.

Degradation of 2,4-dichlorophenol (2,4-DCP) in aqueous by glow discharge electrolysis (GDE) has been investigated. Ultraviolet (UV) absorption spectra, atomic force microscopy (AFM), high performance liquid chromatography (HPLC) and gas chromatogram-mass spectrum (GC/MS) are used to monitor the degradation process and to identify the major oxidation intermediate products. It has been found that 2,4-DCP undergoes a series of intermediate step, which leads to form a number of intermediate products, mainly isomeric chlorophenols and aliphatic acids. These products are further oxidized, eventually, mineralized into CO(2) and Cl(-). A degradation pathway for 2,4-DCP is proposed on the basis of detection of intermediate compounds.

Chlorophenols↗

Catalytic hydrodechlorination of 2,4-dichlorophenol on Pd/Rh/C catalysts.

Catalytic hydrodechlorination of 2,4-dichlorophenol was studied over 0.97% Pd/C, 0.98% Rh/C and 0.8% Pd-0.19% Rh/C catalysts. The catalysts were prepared by incipient wetness impregnation of support and characterized by BET surface area, temperature programmed reduction (TPR) and X-ray diffraction (XRD). The 0.97% Pd/C catalyst, which had the largest crystallite size, was the most active and selective towards the formation of 2- and 4-chlorophenols among three catalysts in liquid phase. Hydrodechlorination activity of carbon-supported catalysts were in the order of Pd/C>Pd/Rh/C>Rh/C. The kinetic equation explained experimental data well and kinetic parameters of three catalysts were provided and discussed.

Algorithms↗

Effects of exposure time and co-existing organic compounds on uptake of atrazine from nutrient solution by rice seedlings (Oryza sativa L.).

Root uptake of atrazine (ATR) by rice seedlings (Oryza sativa L.) from nutrient solution was investigated with exposure periods of 48, 96, and 240h. A similar ATR uptake was carried out with two co-existing organic compounds (o-chlorophenol (CP) and 2,4-dichlorophenol (DCP)) with 48h exposure. In contact with the seedlings, the ATR level in nutrient solution decreased sharply during the early exposure and then reached relatively steady levels after 48h. It was observed that the ATR levels within whole seedlings approached the estimated equilibrium partition limits in about 48h, according to the partition-limited model utilizing the measured plant water and organic matter contents and the ATR partition coefficients with whole seedlings. However, when roots and shoots were consisted separately, the detected ATR levels in roots were lower than estimated equilibrium limit while the levels in shoots exceeded the equilibrium limit. The data with roots suggested the occurrence of rapid ATR degradation in roots. The results with shoots are intrinsically consistent with the suggested complex formation of ATR with free metal ions in shoots. The ATR levels in roots and shoots varied to a moderate extent when the seedlings were exposed to different levels of ATR-CP-DCP mixtures. The variation results presumably from the interference of coexisting CP and DCP and the phytotoxicity of the mixed chemicals.

Atrazine↗

Sorption of phenols onto sandy aquifer material: the effect of dissolved organic matter (DOM).

The influence of dissolved organic matter (DOM) on the sorption of four phenols, 2,4,6-trichlorophenol (2,4,6-TCP), pentachlorophenol (PCP), 2,4-dinitrophenol (2,4-DNP) and 2-methyl-4,6-dinitrophenol (2-M-4,6-DNP), onto sandy aquifer material at different pH values was investigated using flow through column experiments. The pH-dependent sorption of the chlorinated phenols 2,4,6-TCP and PCP was not significantly affected by DOM (measured as dissolved organic carbon, DOC), whereas in the case of nitrophenols a significant lower retardation was found, depending on the DOC concentration and pH value of the aqueous solution. Sorption decreases with increasing DOC concentration, which indicates a binding of these compounds by DOM. The degree of sorption reduction depends on the pH value and increases with increasing fraction of neutral species. The different behaviour of nitrophenols in comparison to the chlorophenols is assumed to be a result of specific charge-transfer interactions. A combined sorption and complex formation model was used to describe the effect of pH and DOC concentration on the sorption of nitrophenols onto aquifer material and to estimate binding coefficients of neutral nitrophenols on DOM.

Adsorption↗

Kinetics and mechanisms of formation of bromophenols during drinking water chlorination: assessment of taste and odor development.

Halophenols are often reported as off-flavor causing compounds responsible for medicinal taste and odor episodes in drinking water. To better understand and minimize the formation of 2-bromophenol and 2,6-dibromophenol which have low odor threshold concentrations (OTCs, 30 and 0.5 ng/L, respectively) a kinetic data base for the chlorination and bromination of phenols was established by combination of kinetic measurements and data from literature. Second-order rate constants for the reactions of chloro- and bromophenols with chlorine and bromine were determined over a wide pH range. The second-order rate constants for bromination of phenols are about three orders of magnitude higher than for chlorination. A quantitative structure activity relationship (QSAR) showed a good comparability of second-order rate constants from this study with those published previously for different phenol derivatives. The quantification of product distribution of the formed halophenols demonstrated that chlorine or bromine attack in ortho position is favored with respect to the para position. A kinetic model was formulated allowing us to investigate the influence of chlorine dose and some water quality parameters such as the concentration of phenol, ammonia, bromide and the pH on the product distribution of halophenols. The kinetic model can be applied to optimize drinking water chlorination with respect to phenol-born taste and odor problems. In general, high chlorine doses lead to low concentrations of intermediate odorous chlorophenols and bromophenols. An increase in the ammonia or phenol concentration leads to a higher consumption of HOCl and therefore greater final concentration of intermediate bromophenols. The presence of higher bromide than phenol concentration also facilitates the rapid bromination pathway which leads to further bromination of 2,6-dibromophenol to higher brominated phenols. Laboratory-scale experiments on taste and odor formation due to the chlorination of phenol- and bromide-containing waters have confirmed the trend of the model calculations.

Bromine↗

Catabolism of pentachlorophenol by a Flavobacterium sp.

The pathway employed for pentachlorophenol (PCP) degradation by an aerobic, chlorophenol-utilizing Flavobacterium sp. was initiated by conversion of PCP to tetrachloro-p-hydroquinone (TCH). 18O labelling experiments demonstrated that the first dechlorination, where a hydroxyl replaced the chlorine at PCP ring position number 4, involved a hydrolytic reaction. Then two reductive dechlorinations of TCH followed to yield firstly trichlorohydroquinone (TrCH) and then 2,6-dichlorohydroquinone (DCH). Thus, the initial steps in catabolism of PCP by the Flavobacterium were: PCP----TCH----TrCH.

Chlorine↗