Reduction of toxicity of antimicrobial compounds by degradation processes using activated sludge, gamma radiation, and UV.

The occurrence and persistence of pharmacologically active compounds in the environment has been an increasingly important issue. The objectives of this study were to investigate the decomposition of aqueous antimicrobial compounds using activated sludge, γ-irradiation, and UV treatment, and to evaluate the toxicity towards green algae, Pseudokirchneriella subcapitata, before and after treatment. Tetracycline (TCN), lincomycin (LMC) and sulfamethazine (SMZ) were used as target compounds. Gamma (γ)-irradiation showed the highest removal efficiency for all target compounds, while UV and activated sludge treatment showed compound-dependent removal efficiencies. TCN and SMZ were well degraded by all three treatment methods. However, LMC showed extremely low removal efficiency for UV and activated sludge treatments. Overall, the algal toxicity after degradation processes was significantly decreased, and was closely correlated to removal efficiency. However, in the case of γ-irradiated TCN, UV and activated sludge treated LMC as well as sludge treated SMZ, the observed toxicity was higher than expected, which indicates the substantial generation of byproducts or transformed compounds of a greater toxicity in the treated sample. Consequently, γ-radiation treatment could be an effective method for removal of recalcitrant compounds such as antibiotics.

Degradation and toxicity assessment of sulfamethoxazole and chlortetracycline using electron beam, ozone and UV.

Recently, the occurrence of antibiotics in sewage treatment plant effluent, as well as drinking water, has raised concern about their potential impacts on the environment and public health. Antibiotics are found in surface and ground waters, which indicate their ineffective removal by conventional wastewater treatment processes. Therefore, advanced oxidation processes (AOPs) have received considerable attention for the removal of antibiotics. This study was conducted to evaluate the degradation and mineralization of antibiotics (sulfamethoxazole and chlortetracycline) using an electron beam, ozone and UV, and the change of toxicity. Also, the electrical energy consumption based on the EE/O parameter (the electrical energy required per order of pollutants removal in 1 m(3) wastewater) was used to quantify the energy cost associated with the different AOPs (electron beam, ozone and UV) for the degradation of antibiotics. The results showed that an electron beam effective for the removals of both sulfamethoxazole and chlortetracycline in aqueous solutions. However, degradation of the target compounds by ozone and UV showed different trends. The oxidation efficiency of each organic compound was very dependent upon the AOP used. Algal toxicity was significantly reduced after each treatment. However, based on the electrical energy, the electron beam was more efficient than ozone and UV. Electron beam treatment could be an effective and safe method for the removal of antibiotic compounds.

Combination of ion exchange system and biological reactors for simultaneous removal of ammonia and organics.

A novel process for a simultaneous removal of ammonia and organics was developed on the basis of ion exchange and biological reactions. From batch experiments, it was found out that NH(4)(+) could be removed effectively by combining cation exchange and biological nitrification showing 0.98 mg N/m(2) ∙ s of a maximum flux. On the other hand, the removal of NO(3)(-) was 3.5 times faster than NH(4)(+) and the maximum flux was calculated to be 3.4 mg N/m(2) ∙ s. The systems for NH(4)(+) and NO(3)(-) removal were combined for establishing the IEBR process. When the process was operated in a continuous mode, approximately 95.8% of NH(4)(+) was removed showing an average flux of 0.22 mg N/m(2) · s. The removal efficiency of total nitrogen was calculated as 94.5% whereas that of organics was 99.5%. It was concluded that the IEBR process would be effectively used for a simultaneous removal of NH(4)(+) and organics.

Simultaneous nitrification and denitrification in a CEM (cation exchange membrane)-bounded two chamber system.

A novel process was developed to induce a simultaneous oxidation of ammonia and denitrification in a single system consisting of two chambers separated by a cation exchange membrane. One was an anoxic chamber and the other was an aerobic chamber. The maximum mass flux via the membrane was calculated as 0.83mg NH(4)(+)-N/m(2)s in a batch test when the initial concentration of NH(4)(+) was 700 mg N/L. And it was observed that NO(3)(-) and NO(2)(-) moved via the membrane in a reverse direction when NH(4)(+) was transported. When the system was operated in a continuous mode by feeding a wastewater containing glucose and NH(4)(+), it was observed that soluble chemical oxygen demand and NH(4)(+) were simultaneously removed showing 99% and 71 approximately 86% of efficiency, respectively. Denitrification occurred in the anoxic chamber and nitrification was carried out in the aerobic chamber.

Carbon source recovery from waste activated sludge by alkaline hydrolysis and gamma-ray irradiation for biological denitrification.

The recovery of an organic carbon source from a waste activated sludge by using alkaline hydrolysis and radiation treatment was studied, and the feasibility of the solubilized sludge carbon source for a biological denitrification was also investigated. The effects of an alkaline treatment and gamma-ray irradiation on a biodegradability enhancement of the sludge were also studied. A modified continuous bioreactor for a denitrification (MLE reactor) was operated by using a synthetic wastewater for 47 days. Alkaline treatment of pH 10 and gamma-ray irradiation of 20 kGy were found to be the optimum carbon source recovery conditions. COD removal of 84% and T-N removal of 51% could be obtained by using the solubilized sludge carbon source through the MLE denitrification process. It can be concluded that the carbon source recovered from the waste activated sludge was successfully employed as an alternative carbon source for a biological denitrification.

TiO2 photocatalytic oxidation mechanism of As(III).

There has been a controversy over the TiO2 photocatalytic oxidation (PCO) mechanism of As(III) for the last several years. The key argument has been whether superoxide (HO2*/O2(-)*) is the main oxidant of As(III) in the UV/TiO2 system. Previously we and other groups have refuted the claim that superoxide plays the main role in the TiO2 PCO of As(III). Nevertheless, thereafter, the superoxide-mediated As(III) oxidation mechanism has been repeatedly claimed, making it difficult to draw a clear conclusion regarding this mechanism. The objective of this study is to draw a unanimous conclusion on the TiO2 PCO mechanism of As(III) and thus finish the controversy regarding this issue. To investigate the correlation between As(III) oxidation and superoxide, both As(V) and H2O2 were measured simultaneously. When excess formic acid (FA) was added as a scavenger of valence band (VB) hole (or *OH) in UV/TiO2 or vacuum-UV lamp irradiation (lambda = 185 + 254 nm), As(III) oxidation was greatly inhibited while H2O2 generation was promoted. Since H2O2 is photochemically produced through the disproportionation of superoxide, this result definitely shows that superoxide has little role in the oxidation of As(III) not only in UV/TiO2 but also in other advanced oxidation processes (AOPs). Interestingly, not only FA (a scavenger of VB hole) but also methanol (a scavenger of adsorbed *OH) showed an inhibitory effect on the TiO2 PCO of As(III). Excess methanol retarded the TiO2 PCO of As(III) moderately but not completely, which indicates that adsorbed *OH also plays a significant role along with VB hole in the TiO2 PCO of As(III). Although the conclusion is not based on the rate constant between As(III) and superoxide but derived from indirect inference from the experimental data, this study provides convincing evidence to support that adsorbed *OH and VB hole are the main oxidants in the TiO2 PCO mechanism of As(III).

Decomposition and mineralization of cefaclor by ionizing radiation: kinetics and effects of the radical scavengers.

There has been recent growing interest in the presence of antibiotics in different environmental sectors. One considerable concern is the potential development of antibiotic-resistant bacteria in the environment, even at low concentrations. Cefaclor, one of the beta-lactam antibiotics, is widely used as an antibiotic. Kinetic studies were conducted to evaluate the decomposition and mineralization of cefaclor using gamma radiation. Cefaclor, 30 mg/l, was completely degraded with 1,000 Gy of gamma radiation. At a concentration of 30 mg/l, the removal efficiency, represented by the G-value, decreased with increasing accumulated radiation dose. Batch kinetic experiments with initial aqueous concentrations of 8.9, 13.3, 20.0 and 30.0mg/l showed the decomposition of cefaclor using gamma radiation followed a pseudo first-order reaction, and the dose constant increased with lower initial concentrations. At a given radiation dose, the G-values increased with higher initial cefaclor concentrations. The experimental results using methanol and thiourea as radical scavengers indicated that ()OH radicals were more closely associated with the radiolytic decomposition of cefaclor than other radicals, such as e(aq)(-) or ()H. The radical scavenger effects were tested under O(2) and N(2)O saturations for the enhancement of the TOC percentage removal efficiencies in the radiolytic decomposition of cefaclor. Under O(2) saturation, 90% TOC removal was observed with 100,000 Gy. Oxygen is well known to play a considerable role in the degradation of organic substances with effective chain reaction pathways. According to the effective radical reactions, the enhanced TOC percentage removal efficiencies might be based on the fast conversion reactions of e(aq)(-) and ()H with O(2) into oxidizing radicals, such as O(2)(-) and HO(2)(), respectively. 100% TOC removal was obtained with N(2)O gas at 20,000 Gy, as reducing radicals, such as e(aq)(-) and ()H, are scavenged by N(2)O and converted into ()OH radicals, which have strong oxidative properties. The results of this study showed that gamma irradiation was very effective for the removal of cefaclor in aqueous solution. The use of O(2) or N(2)O, with radiation, shows promise as effective radical scavengers for enhancing the TOC or COD removal efficiencies in pharmaceutical wastewaters containing antibiotics. However, the biological toxicity and interactions between various chemicals during the radiolytic treatment, as well as treatments under conditions more representative of real wastewater will require further studies.

Decomposition of 2,4,6-trinitrotoluene (TNT) by gamma irradiation.

The purpose of this study was to evaluate the potential of gamma irradiation to decompose 2,4,6-trinitrotoluene (TNT) in an aqueous solution; the concentration range of the TNT solution was 0.11-0.44 mmol/L. The decomposition rate of TNT by gamma irradiation was pseudo-first-order kinetic over the applied initial concentrations. The dose constant was strongly dependent on the initial concentration of TNT. Increasing the concentration of dissolved oxygen in the solution was more effective on the decomposition of TNT as well as its mineralization. The required irradiation dose to remove 90% of initial TNT (0.44 mmol/L) was 58, 41, 32, 28, and 25 kGy at the dissolved oxygen concentration of 0.025, 0.149, 0.3, 0.538, and 0.822 mmol/L, respectively. However, TOC still remained as 30% of the initial TOC (3.19 mmol/L) when 200 kGy irradiation dose was applied to the TNT solution (0.44 mmol/L) containing dissolved oxygen of 0.822 mmol/L. The removal of the TNT was more efficient at a pH below 3 and at a pH above 11 than at neutral pH (pH 5-9). The required irradiation dose to remove over 99% of the initial TNT (0.44 mmol/L) was 39, 76, and 10 kGy at pH 2, 7, and 13, respectively. The dose constant was increased 1.6-fold and over 15.6-fold at pH 2 and 13, respectively, compared to that at pH 7. When an irradiation dose of 200 kGy was applied, the removal efficiencies of the TOC (initial concentration 3.19 mmol/L) were 91, 46, and 53% at pH 2, 7, and 13, respectively. Ammonia and nitrate were detected as the main nitrogen byproducts of TNT, and glyoxalic acid and oxalic acid were detected as organic byproducts.

Comparative study of H(2)O(2) and O3 effects on radiation treatment of TCE and PCE.

The effects of H(2)O(2) and O(3) on the decomposition of trichloroethylene (TCE) and perchloroethylene (PCE) by gamma-rays (gamma-rays) were investigated in this work. The combined gamma-rays/O(3) process showed a synergistic effect and enhanced the removal of TCE and PCE compared with gamma-rays alone, but, the gamma-rays/H(2)O(2) process did not increase the removal. This interesting result was successfully identified by an electron paramagnetic resonance spectroscopy/spin-trapping method that can quantify hydroxyl radicals, which is directly related to the efficiency of TCE and PCE decomposition. For gamma-rays/H(2)O(2) system, there was no difference of hydroxyl radical production between gamma-rays alone and gamma-rays/H(2)O(2). This indicates gamma-rays cannot activate H(2)O(2) to produce hydroxyl radicals and this causes no increase of TCE and PCE removals. To the contrary, the production of hydroxyl radicals was obviously increased in the case of gamma-rays/O(3) process. This suggests additional hydroxyl radicals are produced from the reaction of O(3) with the irradiation products of water such as hydrated electrons, hydrogen atoms, etc. and this accelerates the removal of TCE and PCE.

EPR investigation on the efficiency of hydroxyl radical production of gamma-irradiated anatase and bentonite.

Anatase and bentonite were treated by gamma rays in various conditions, and the change of the catalysts was characterized by electron paramagnetic resonance spectroscopy. Anatase gave four peaks with g(parallel) = 1.951 g(perpendicular) = 1.973, g = 1.992 and 2.005. The height of the four peaks was directly proportional to the efficiency of hydroxyl radical production, and anatase treated by gamma rays in alkaline condition showed the most efficient production. Bentonite gave a peak with g = 2.005. In contrast to anatase, the peak height was inversely proportional to the efficiency of hydroxyl radical production, and non-treated bentonite was the most efficient catalyst. Furthermore, the efficiency of hydroxyl radical production of the catalysts significantly influenced the decomposition of trichloroethylene and perchloroethylene by gamma rays.

Effect of dissolved metal ions on PCE decomposition by gamma-rays.

This study investigates the effect of initial tetrachloroethylene (PCE) concentration, irradiation dose and dissolved metal ions such as Cr3+, Mn2+, Fe3+, Co2+, Ni2+, Cu2+ and Zn2+ on removal of PCE by gamma irradiation. The amount of removed PCE decreased with increase in initial PCE concentration and increased with increase in irradiation dose. PCE removal reached a maximum in the presence of Fe3+, while Cu2+ strongly hindered PCE decomposition. Except for Cu2+, the amount of removed PCE in the presence of metal ions was linearly dependent on the standard reduction potential of the metal ions. The extraordinary inhibition of Cu2+ in PCE removal was caused by the action of Cu2+ as a strong *OH scavenger, that was directly confirmed by electron paramagnetic resonance spectroscopy.