Synergetic effects of photo-oxidation and biodegradation on failure behavior of polyester coating in tropical rain forest atmosphere

This work aimed to study the comprehensive effects of photo-oxidation and biodegradation on different failure stages of polyester coatings,which were exposed to the tropical rainforest atmosphere.The surface morphology,aging products,local aging characteristics and electrochemical behavior of the coatings were characterized with scanning electron microscope(SEM),fourier transform infrared spectroscopy(FTIR),electrochemical impedance spectroscopy(EIS)and high-resolution dispersive Raman microscope.The results showed that the surface of coatings became rougher and fungal hyphae distributed more densely on surface with the increasing of exposure time.From the aspect of polymer structure,the ultraviolet radiation destroyed the main chain of polyester through the photo-oxidation process,resulting in the breakage of aliphatic ester bonds and the formation of esters.Further,the metabolites of fungi can promote the hydrolysis of oligomers produced by the photo-oxidation.In a short,the photo-oxidation could facilitate the biodegradation of the coating.With the synergistic effect of UV photo-oxidation and fungal biodegradation,a rapid diffusion tunnel between the coating surface and the metal substrate was established at the pore defects of the coating,which finally accelerated the corrosion failure process of the coating.The main corrosion products includeα-Fe₂O₃,ZnO and Zn₅(OH)₆(CO₃)₂.     

Evaluation of anaerobic co-digestion of spent brewery grains and an azo dye

Anaerobic batch biodegradation of spent brewery grains (SBG) was investigated in the presence of co-substrates and a monoazo dye (Acid Orange 7 – AO7) under mesophilic and thermophilic regimes. The highest values for the yield coefficient of biogas (STP) on substrate (Y_bs) were obtained under mesophilic conditions (0.381–0.516 Lbiogas/g COD_removed and 0.147 to 0.475 L_biogas/g COD_removed for mesophilic and thermophilic regimes, respectively). A stimulation of the degradation of SBG associated with microbial growth was observed in the presence of co-substrates (glucose and acetate). Supplemented co-substrates also lowered the residual COD leading to an increase in the COD removal efficiency, particularly under thermophilic regime (from 41% to 70%). Although biogas yield (Y_bs) indicates a decrease in the presence of the dye, suggesting that it has inhibitory effects, the overall COD removal was not significantly altered. An increase of colour removal was observed when the temperature of the operation was increased (87 ± 2% and 93 ± 1% for mesophilic and thermophilic reactors, respectively), which could be explained by both faster adsorption and biotic reductive cleavage of azo dye bond mechanisms. These results indicate that raw SBG is more prone to biodegradation under an anaerobic mesophilic regime; hence its bio-energetic valorisation is possible.     

Biodegradable and thermostable synthetic hyperbranched poly(urethane-urea)s as advanced surface coating materials

Aliphatic hyperbranched poly(urethane-urea)s with different weight percentages of branch generating moiety were synthesized by a one pot A₂ + BC₂ approach. Isophorone diisocyanate was used as the A₂ type monomer, while a tri-functional dihydroxyamine compound synthesized from ?-caprolactam and diethanol amine acted as the BC₂ monomer. Evidence supporting the hyperbranched structure of the synthesized poly(urethane-urea) was obtained from ¹H NMR spectra. FTIR study confirmed the nature and extent of hydrogen bonding present in this novel macromolecule. A Gaussian band fitting procedure of the IR band at amide-I region showed that the extent of hydrogen bonding increases with the increase of weight percentage of the tri-functional compound. The tensile strength, elongation at break, impact resistance, scratch hardness and gloss followed an increasing trend with the same. The thermal degradation of the hyperbranched poly(urethane-urea) was found to be dependent on the weight percentage of the BC₂ type moiety. The kinetics of thermal degradation studied by the Ozawa method showed that the activation energy required for thermal degradation of hyperbranched polymer is higher than its linear polyurethane analog. The synthesized polymer was found to be biodegradable by Pseudomonas aeruginosa bacteria. The study showed superiority of the hyperbranched structure over the linear one. Thus the results indicated the potential usage of the studied hyperbranched poly(urethane-urea) as an advanced surface coating material.     

Combined advanced oxidation and biodegradation of industrial effluents from the production of stilbene-based fluorescent whitening agents

Three different industrial wastewaters from the production of stilbene-based fluorescent whitening agents were investigated with regard to the applicability of advanced oxidation processes combined with biodegradation. Oxidation processes included the application of ozone, hydrogen peroxide, UV-radiation and Fenton's reagent (Fe(2+)/H(2)O(2)). Characterization of the combined chemical-biological treatment was done by sum parameters and HPLC analysis. In addition, toxicity was determined using the luminescence inhibition test. Results showed that processes producing OH-radicals without the need of UV-irradiation proved to be suited for the oxidation of all three wastewaters. H(2)O(2)/UV processes were ineffective due to the high inner filter effect of the effluents. Comparing the combined oxidative-biological process with biological treatment, the applied pre-oxidation steps did not always lead to a significant improvement of the biological degradation. In one case, an inverted treatment starting with biodegradation followed by oxidation turned out to be the preferable procedure. After oxidation with ozone or ozone combined with UV-irradiation, an increase in toxicity was partly observed indicating the formation of toxic intermediate products. In some cases samples had to be diluted before the biodegradation step to achieve a better biodegradability.     

Elimination of beta-blockers in sewage treatment plants

beta-Blockers are used to treat high blood pressure as well as patients recovering from heart attacks. In several studies, they were detected in surface water, thus indicating incomplete degradability of these substances in sewage treatment plants (STPs). In this study, we determined the sorption coefficients (K(D)) and degradation rates of the four beta-blockers sotalol, atenolol, metoprolol and propranolol in sludge from an STP operating with municipal wastewater. The sorption coefficients (K(D), standard deviations in brackets) were determined as 0.04(+/-0.035), 0.04(+/-0.033), 0.00(+/-0.023) and 0.32(+/-0.058) Lg(-1)(COD), and the pseudo-first-order degradation rate constants were estimated to be 0.29(+/-0.02), 0.69(+/-0.05), 0.58(+/-0.05) and 0.39(+/-0.07) Ld(-1)g(-1)(COD) for sotalol, atenolol, metoprolol and propranolol, respectively. These values translate into a typical elimination in STPs (sludge concentrations of 4g(COD)L(-1) and a hydraulic retention time of 6h) of 25%, 37%, 44% and 50% for sotalol, propranolol, metoprolol and atenolol, respectively. These results are also confirmed by measurements in two municipal STPs for atenolol, sotalol and propranolol. The estimated eliminations are slightly too high for metoprolol.     

Metabolites from the biodegradation of di-ester plasticizers by Rhodococcus rhodochrous

The plasticizers di-2-ethylhexyl phthalate (DEHP) and di-2-ethylhexyl adipate (DEHA) are ubiquitous in the environment and undergo partial biodegradation in the presence of soil micro-organisms. The validity of a proposed pathway for the degradation of these plasticizers by Rhodococcus rhodochrous has been confirmed by the identification of 2-ethylhexanal in gas phase emissions. Complete analyses of the aqueous and gas phases were able to account for more than 98% of the 2-ethylhexanol component of the DEHA added at the beginning of a growth study. Of this, 25% was either 2-ethylhexanol or 2-ethylhexanal that had been stripped into the gas phase and, at most, only 2% of the 2-ethylhexanol component could have been removed by mineralization. It is concluded that plasticizers are of significant environmental concern due to the resistance of the metabolites to biodegradation and their known health impacts. Two of the metabolites are of added concern due to their volatility and their potential impact on indoor air quality.     

Comparison of 2-chlorobenzoic acid biodegradation in a membrane bioreactor by B. cepacia and B. cepacia bearing the bacterial hemoglobin gene

Degradation of 2-chlorobenzoic acid (2-CBA), a model recalcitrant chlorinated organic compound, by pure cultures of Burkholderia cepacia strain DNT with (transformed B. cepacia) and without (untransformed B. cepacia) the bacterial hemoglobin (Vitreoscilla hemoglobin, VHb) gene, vgb, was investigated in parallel membrane bioreactors (MBRs). This was done aseptically to prevent contamination during the operation of the MBRs. The objective was to determine whether the degradation of 2-CBA by cometabolism, using acetate as a primary carbon source, under hypoxic conditions might be enhanced for vgb-bearing cells in MBRs. The 2-CBA removal efficiency of transformed B. cepacia (97-99%) was slightly higher than that of untransformed B. cepacia (95-99%) at all stages. The average amount of chloride released from 2-CBA by transformed cells was also higher than for untransformed cells, 92-96% compared to 64-84% of the maximum theoretical amount, the exact value depending on the operating conditions. These results indicate that 2-CBA degradation/transformation is not accompanied by the stoichiometric release of chloride for the untransformed strain. The difference between percentages of 2-CBA removal and chloride release by untransformed cells was attributed to persistence, under hypoxic conditions, of the 2-CBA chlorine atom in 2-CBA metabolites. Growth of transformed cells was also significantly enhanced under hypoxic conditions compared to untransformed cells. For varying media compositions, the transformed cells reached higher cell densities (3.2-5.4 g/L) relative to untransformed cells (2.8-4.7 g/L) at food to microorganism ratios ranging from 0.44-0.59 to 0.38-0.49 g COD/g biomass-d The observed yields thus ranged from 0.16-0.20 and 0.15-0.18 g TSS/g COD for untransformed and transformed cells, respectively. The value of the yield depended on medium composition. The MBR system using vgb-containing B. cepacia maintained a high biomass concentration without oxygen limitations and provided cell-free effluent. Hence, it may be useful for treating high volumes of water contaminated with low levels of recalcitrant organics.     

Biodegradation of nonylphenol polyethoxylates under sulfate-reducing conditions

Biodegradation behavior of nonylphenol polyethoxylates (NPEOs) under sulfate-reducing conditions was investigated. The results showed that NPEOs were readily degraded under sulfate-reducing conditions. These compounds were degraded via sequential removal of ethoxyl units to nonylphenol (NP) without forming carboxylated intermediates under sulfate-reducing conditions. The biodegradation of NPEOs under sulfate-reducing conditions was not inhibited even at very high initial concentrations of NPEOs. The maximum removal rate increased about 1.3 microM d(-1) for each 10 micromol increase in initial concentration. The decrease in temperature caused a sharp decrease in the removal efficiency of NPEOs. The temperature coefficient (Phi) for the biodegradation of NPEOs under sulfate-reducing conditions was 0.008. Severe accumulation of NP and short-chain NPEOs occurred when most NPEOs were removed and this accumulation led to an increase in the estrogenic activity. The highest estrogenic activity appeared on day 21 when the total concentration of these metabolites reached its top (18.03+/-4.73 microM). NP could inhibit the biodegradation of NPEOs under sulfate-reducing conditions only at relatively high concentration. These findings are of major environmental importance in terms of the environmental behavior of NPEO contaminants in natural environment.     

Evaluation and modeling of benzalkonium chloride inhibition and biodegradation in activated sludge

The inhibitory effect and biodegradation of benzalkonium chloride (BAC), a mixture of alkyl benzyl dimethyl ammonium chlorides with different alkyl chain lengths, was investigated at a concentration range from 5 to 20 mg/L and different biomass concentrations in an activated sludge system. A solution containing glucose and mineral salts was used as the wastewater in all the assays performed. The inhibition of respiratory enzymes was identified as the mode of action of BAC as a result of oxygen uptake rate analysis performed at BAC concentrations ranging between 5 and 70 mg/L. The glucose degradation in the activated sludge at different BAC and biomass concentrations was well-described with Monod kinetics with competitive inhibition. The half-saturation inhibition constant (K_I) which is equivalent to EC₅₀ of BAC for the activated sludge tested ranged between 0.12 and 3.60 mg/L. The high K_I values were recorded at low BAC-to-biomass ratios, i.e. less than 10 mg BAC/g VSS, at which BAC was almost totally adsorbed to biomass and not bioavailable. BAC degradation started as soon as glucose was totally consumed. Although BAC was almost totally adsorbed on the biomass, it was degraded completely. Therefore, BAC degradation was modeled using two-phase biodegradation kinetics developed in this study. This model involves rapid partitioning of BAC to biomass and consecutive degradation in both aqueous and solid phases. The aqueous phase BAC degradation rate was twenty times, on average, higher than the solid phase degradation rate. The specific aqueous (k_I1) and solid (k_I2) phase BAC utilization rate constants were 1.25 and 0.31 mg BAC/g VSS h, respectively. The findings of this study would help to understand the reason of extensive distribution of quaternary ammonium compounds in wastewater treatment plant effluents and in natural water systems although QACs are biodegradable, and develop strategies to avoid their release and accumulation in the environment.     

Biodegradation of agricultural herbicides in sequencing batch reactors under aerobic or anaerobic conditions

This study investigated the biodegradability of the herbicides isoproturon and 2,4-dichlorophenoxyacetic acid (2,4-D) in sequencing batch reactors (SBRs). Two laboratory-scale (2L liquid volume) SBRs were employed: one reactor performing under aerobic and the other under anaerobic conditions. The aerobic SBR was operated at an ambient temperature (22+/-2 degrees C), while the anaerobic SBR was run in the lower mesophilic range (30+/-2 degrees C). Each bioreactor was seeded with a 3:1 mixture (by weight) of fresh sludge and biomass that had been previously exposed to both herbicides. The effect of herbicide concentration on either treatment process was explored at a hydraulic retention time (HRT) of 48 h, using glucose as a supplemental carbon substrate. Although no isoproturon degradation was observed in either system during the study, complete 2,4-D removal occurred after an acclimation period of approximately 30 d (aerobic SBR) and 70 d (anaerobic SBR). The aerobic reactor achieved complete 2,4-D utilization at feed concentrations up to 500 mg/L. A further increase to 700 mg/L, however, proved to be inhibitory since 2,4-D biodegradation was negligible. On the other hand, the anaerobic SBR was able to degrade 120 mg/L of 2,4-D, which corresponds to 40% of the maximum feed concentration applied. Moreover, glucose was consumed first throughout the experiment in a sequential utilization pattern relating to 2,4-D, with biodegradation of both substrates following closely first-order kinetics.