A.F. Mohedano

Semicontinuous Fenton oxidation of phenol in aqueous solution. A kinetic study.

This work investigates the Fenton oxidation of phenol in a semicontinuous reactor where the overall amount of H(2)O(2) is distributed as a continuous feed upon the reaction time. The experiments were carried out at 25 degrees C and atmospheric pressure, with 100mg/L initial phenol concentration and iron dosages from 1 to 100 mg/L. H(2)O(2) aqueous solution was continuously fed during 4h reaction time up to an overall dose varying within the range of 500-5000 mg/L. The results in terms of evolution of phenol, H(2)O(2) and intermediates, as well as TOC abatement were compared with those obtained in conventional batch operation. It was found that the oxidation rates for phenol and intermediates were lower when adding the H(2)O(2) continuously. However, a higher abatement of TOC was reached at the end of the 4-h reaction time, in spite of a similar overall H(2)O(2) consumption. This is the result of a more efficient OH generation throughout the semicontinuous process, favouring the reaction with the organic species and reducing the occurrence of competitive scavenging reactions involving Fe(2+), H(2)O(2) and OH. Two kinetic models were proposed, one for describing the evolution of phenol, aromatics and H(2)O(2) and the other for TOC. The influence of the operating conditions on the kinetic constants was also studied, looking for the optimal conditions in terms of both, environmental and economic points of view.

Cometabolic biodegradation of 4-chlorophenol by sequencing batch reactors at different temperatures

The simultaneous removal of 4-chlorophenol (4-CP) and phenol in lab-scale sequencing batch reactors at different temperatures has been studied. Phenol feed concentration was fixed at 525 mg/L and 4-CP concentration was increased from 105 to 2100 mg/L at a constant hydraulic residence time (HRT) of 10.5 d. Complete phenol and 4-CP biodegradation was achieved during the aerobic stage working with 4-CP concentrations up to 1470 mg/L in the feed. Both 4-CP and phenol specific initial removal rates were strongly affected by 4-CP feed concentration and temperature. Only at the highest temperature tested (35 degrees C) it was possible to increase the maximum assimilative 4-CP concentration by the biological sludge up to 2100 mg/L, and a significant reduction of the ecotoxicity of the effluents was observed. 4-chlorocatechol (4-CC) was identified as the major intermediate in the aerobic cometabolic 4-CP degradation, being the ecotoxicity of that species substantially lower than that of 4-CP.

Enhancement of cometabolic biodegradation of 4-chlorophenol induced with phenol and glucose as carbon sources by Comamonas testosteroni

The biological degradation of phenol and 4-chlorophenol (4-CP) by Comamonas testosteroni CECT 326T has been studied. Phenol and 4-CP were treated alone as a sole carbon and energy source, but only phenol was completely degraded by C. testosteroni. Since the presence of cosubstrates can enhance the toxic compounds removal by pure cultures, phenol and glucose were added as growth substrates for cometabolic transformation of 4-CP. High efficiencies were obtained in all the experiments carried out in presence of both cosubstrates. In spite of the fact that the addition of glucose reduced the lag phase of 4-CP removal, lower phenol concentrations were required to obtain the same degradation efficiencies. The cometabolic transformation of 4-CP was closely related with the extent of phenol removal. The values of the 4-CP/biomass concentration ratio (S/X) obtained for discriminating between complete (S/X ≤ 0.11) and partial 4-CP (S/X ≥ 0.31) transformation showed a narrower range than that reported in the literature. The extent of the cometabolic 4-CP transformation in the presence of phenol could be further enhanced by using glucose as an additional carbon and energy source. However, no significant influence of glucose concentration on 4-CP removal was observed over the concentration range studied.

Comparison of UASB and EGSB performance on the anaerobic biodegradation of 2,4-dichlorophenol

The anaerobic degradation of 2,4-dichlorophenol (2,4-DCP) in upflow anaerobic sludge blanket (UASB) and expanded granular sludge bed (EGSB) reactors using glucose as main carbon source was studied. The performance of both systems was compared in terms of 2,4-DCP and COD removal efficiencies, methane production, stability, granular sludge adaptability as well as reversion of the bacterial inhibition. Both organic and 2,4-DCP loading rates were incrementally varied through the experiments. With loading rates of 1.9 gCODL(-1)d(-1) and 100mg 2,4-DCP L(-1)d(-1), 75% and 84% removal efficiencies of this compound, accompanied by COD consumption efficiencies of 61% and 80% were achieved in the UASB and EGSB reactors, respectively. In these conditions, methane production reached 0.088 L CH(4)g(-1) COD in the EGSB reactor whereas in the UASB reactor was almost negligible. Decreasing the 2,4-DCP loading rate to 30 mgL(-1)d(-1) an improvement in the methane production was observed in both reactors (methanogenic activity of 0.148 and 0.192 L CH(4)g(-1) COD in UASB and EGSB reactors, respectively). Efficiency of dechlorination was improved in both reactors from around 30% to 80% by reducing to one-half the COD due to a decreasing of the 4-chlorophenol concentration accumulated in the effluents of both reactors. The dechlorination efficiency of the UASB reactor was dramatically inhibited at a 2,4-DCP feed concentration above around 210 mgL(-1) because of 2,4-DCP accumulation in the effluent. SEM studies revealed no significant morphological changes in the sludge granules.

Hydrodechlorination of 4-chlorophenol in water with formic acid using a Pd/activated carbon catalyst

This work reports on the feasibility of hydrodechlorination as a treatment technique for chlorophenols-bearing wastewaters using formic acid as a hydrogen source. 4-Chlorophenol (4-CPhOH) has been used as target compound and the experiments were carried out in batch and continuous mode with a commercial activated carbon-supported Pd (0.5 wt.%) catalyst. The variables studied in the batch runs were HCOOH/4-CPhOH molar ratio (10-1000), temperature (25-75 degrees C) and catalyst concentration (250-1000 mg/L). The continuous experiments were performed in a fixed bed reactor where aqueous solutions of formic acid and 4-CPhOH with molar ratios between 50 and 100 were continuously fed to the reactor, at different space-time values in the range of 10.7-42.8 kg(cat)h/mol. Reaction temperatures from 35 to 100 degrees C were tested and the pressure was fixed at 2.5bar. Conversion values above 99% for 4-CPhOH were obtained in batch experiments, but using a HCOOH/4-CPhOH molar ratio as high as 500. Moreover, most of the phenol produced was adsorbed on the catalyst. Continuous runs were performed to evaluate the efficiency of the catalyst under lower HCOOH/4-CPhOH ratios and to explore the possibility of converting phenol to more hydrogenated products. The results indicated that the HCOOH/4-CPhOH molar ratios needed were an order of magnitude lower than those required in batch runs to achieve conversions of 4-CPhOH close to 95%. Besides, phenol was not the only reaction product formed, since a more hydrogenated product such as cyclohexanone was detected in the effluent, which indicates additional hydrogenation of phenol in contrast to the behaviour observed in batch experiments. A loss of activity was observed in the continuous runs after 20-30 h on stream.

Degradation of chlorophenoxy herbicides by coupled Fenton and biological oxidation

A combined treatment for the degradation of the chlorophenoxy herbicides 2,4-D and MCPA in water by means of Fenton and biological oxidation has been studied. The chemical oxidation step was necessary to achieve an efficient removal of these pollutants due to their toxicity and low biodegradability. Aqueous herbicide solutions (180mgL(-1)) were subjected to Fenton oxidation upon different H2O2 doses (from the theoretical stoichiometric amount referred to initial COD to 20% of this value). The toxicity and biodegradability tests of the Fenton effluents suggested that the ones resulting upon treatment with 80% and 60% of stoichiometric H2O2 were the optimal for subsequent biological treatment dealing with 2,4-D and MCPA, respectively. These effluents were treated in a sequencing batch reactor achieving nearly 90% conversion of organic matter measured as COD.

Coupling Fenton and biological oxidation for the removal of nitrochlorinated herbicides from water.

The combination of Fenton and biological oxidation for the removal of the nitrochlorinated herbicides alachlor, atrazine and diuron in aqueous solution has been studied. The H2O2 dose was varied from 20 to 100% of the stoichiometric amount related to the initial chemical oxygen demand (COD). The effluents from Fenton oxidation were analyzed for ecotoxicity, biodegradability, total organic carbon (TOC), COD and intermediate byproducts. The chemical step resulted in a significant improvement of the biodegradability in spite of its negligible or even slightly negative effect on the ecotoxicity. Working at 60% of the stoichiometric H2O2 dose allowed obtaining highly biodegradable effluents in the cases of alachlor and atrazine. That dose was even lower (40% of the stoichiometric) for diuron. The subsequent biological treatment was carried out in a sequencing batch reactor (SBR) and the combined Fenton-biological treatment allowed up to around 80% of COD reduction.

Cosmetic wastewater treatment by upflow anaerobic sludge blanket reactor

Anaerobic treatment of pre-settled cosmetic wastewater in batch and continuous experiments has been investigated. Biodegradability tests showed high COD and solid removal efficiencies (about 70%), being the hydrolysis of solids the limiting step of the process. Continuous treatment was carried out in an upflow anaerobic sludge blanket reactor. High COD and TSS removal efficiencies (up to 95% and 85%, respectively) were achieved over a wide range of organic load rate (from 1.8 to 9.2g TCODL(-1)day(-1)). Methanogenesis inhibition was observed in batch assays, which can be predicted by means of a Haldane-based inhibition model. Both COD and solid removal were modelled by Monod and pseudo-first order models, respectively.

Effect of 2,4,6-trichlorophenol on the microbial activity of adapted anaerobic granular sludge bioaugmented with Desulfitobacterium strains

The anaerobic degradation of 2,4,6-trichlorophenol (246TCP) has been studied in batch experiments. Granular sludges previously acclimated to 2,4-dichlorophenol (24DCP) and then adapted to at a load of 330 μM 246TCPd(-1) in two expanded granular sludge bed (EGSB) reactors were used. One of the reactors had been bioaugmented with Desulfitobacterium strains whereas the other served as control. 246TCP was tested at concentrations between 250 and 760 μM. The study focused on the fate of both fermentation products and chlorophenols derived from dechlorination of 246TCP. This compound mainly affected the biodegradation of acetate and propionate, which were inhibited at 246TCP concentrations above 380 μM. Lactate and ethanol were also accumulated at 760 μM 246TCP. Methanogenesis was strongly inhibited at 246TCP concentrations higher than 380 μM. A diauxic production of methane was observed, which can be described by a kinetic model in which acetoclastic methanogenesis was inhibited, whereas hydrogenotrophic methanogenesis was hardly affected by 246TCP. The similarity of the kinetic parameters obtained for the control and the bioaugmented sludges (K(i)=175-200 μM 246TCP and n=7) suggests that methanogenesis is not affected by the bioaugmentation. Moreover, the 246TCP dechlorination occurred mainly at ortho position, successively generating 24DCP and 4-chlorophenol (4CP), which was identified as final product. The bioaugmentation does not significantly improve the anaerobic biodegradation of 246TCP. It has been shown that the active biomass is capable of bioaccumulating 246TCP and products from dechlorination, which are subsequently excreted to the bulk medium when the biomass becomes active again. A kinetic model is proposed which simultaneously explains 246TCP and 24DCP reductive dechlorinations and includes the 246TCP bioaccumulation. The values of the kinetic parameters for 246TCP dechlorination were not affected by bioaugmentation (V(max)=5.3 and 5.1 μM h(-1) and K(s)=5.8 and 13.1 μM for control and bioaugmented sludges, respectively).

Inhibition of methanogenesis by chlorophenols: a kinetic approach.

Chlorophenols exert a crucial effect on the methanogenesis, considerably reducing both maximum methane potential and methanogenic rates. However, there is not enough information about the kinetic mechanism of chlorophenols toxicity on the methanogenesis, which is a key aspect for the control of the anaerobic digesters because of the sensitivity and the potential for energy recovery derived from methane release. The International Water Association-Anaerobic Digestion Model No. 1 (IWA-ADM1) can be adapted to a wide range of situations by updating or changing the equations in the model. The present study proposes a general kinetic model for methanogenesis. This model has been applied to predict the inhibition of methanogenesis by chlorophenols, and it can be used for updating the IWA-ADM1 when treating inhibitory compounds. The model was calibrated and validated using a wide broad of experimental sets of data of methane production by granular sludge in the presence of 2,4-dichlorophenol (24 DCP), 2,4,6-trichlorophenol (246TCP) and pentachlorophenol (PCP) in batch assays. A lag-phase of the effect of chlorophenols on the methanogenesis by non-adapted sludge was detected and modeled by the kinetic model proposed. In addition, the inhibitory effect of PCP was more pronounced on the acetoclastic methanogenesis than on the hydrogenotrophic one. Non-competitive and uncompetitive inhibition types were detected using 24 DCP and 246 TCP, whereas a suicide or irreversible inhibition type was observed in the case of PCP. Values of inhibition constants considerably varied depending on the chlorophenol used, between 45 mg24DCPL(-1), 41-51 mg246TCPL(-1) and 0.9-7.8 mgPCPL(-1). The higher toxicity of PCP is related with its hydrophobicity, which was determined by adsorption tests and using partition coefficients n-octanol/water. Modeling was accompanied by high statistical support in all cases, which confirmed the validation of the model proposed.