Application of gaseous ozone for inactivation of Bacillus subtilis spores

The effectiveness of gaseous ozone (O3) as a disinfectant was tested on Bacillus subtilis spores, which share the same physiological characteristics as Bacillus anthracis spores that cause the anthrax disease. Spores dried on surfaces of different carrier material were exposed to O3 gas in the range of 500-5000 ppm and at relative humidity (RH) of 70-95%. Gaseous O3 was found to be very effective against the B. subtilis spores, and at O3 concentrations as low as 3 mg/L (1500 ppm), approximately 3-log inactivation was obtained within 4 hr of exposure. The inactivation curves consisted of a short lag phase followed by an exponential decrease in the number of surviving spores. Prehydration of the bacterial spores has eliminated the initial lag phase. The inactivation rate increased with increasing O3 concentration but not >3 mg/L. The inactivation rate also increased with increase in RH. Different survival curves were obtained for various surfaces used to carry spores. Inactivation rates of spores on glass, a vinyl floor tile, and office paper were nearly the same. Whereas cut pile carpet and hardwood flooring surfaces resulted in much lower inactivation rates, another type of carpet (loop pile) showed significant enhancement in the inactivation of the spores.     

Assessment of Bacillus subtilis spores as a possible bioindicator for evaluation of the microbicidal efficacy of radiation processing of water.

Gamma and electron-beam irradiation of Bacillus subtilis spores suspended in different types of water was studied to evaluate the inactivation of the spores and assess their possible use as a bioindicator for radiation processing. We found that the inactivation proceeded endogenously, being dose-rate-dependent and affected by oxygen. The radiation resistance of the suspended spores was found to be rather high; therefore, B. subtilis spores used as a bioindicator for efficiency of water treatment by radiation under practical conditions might result in the spores being overly conservative surrogates for pathogenic microorganisms. Moreover, the doserate dependency impedes the use of the spores as a bioindicator. Thus, B. subtilis spores cannot be recommended as a bioindicator for evaluation of the microbicidal efficacy of ionizing radiation processing of water.     

Homogeneous degradation of 1,2,9,10-tetrachlorodecane in aqueous solutions using hydrogen peroxide, iron and UV light

The homogeneous degradation of the polychlorinated n-alkane, 1,2,9,10-tetrachlorodecane (T4C10), was studied in aqueous solutions of hydrogen peroxide, including Fenton and photo-Fenton reaction conditions. All solutions were adjusted to a pH of 2.8 and an ionic strength of 0.1 M NaClO4 prior to photolysis. T4C10 (2 x 10(-6) M) was substantially degraded by the H2O2/UV system (1.0 x 10(-2) M H2O2), with 60% disappearance in 20 min of irradiation in a photoreactor equipped with 300 nm lamps of light intensity 3.6 x 10(-5) Ein L(-1) min(-1) (established by ferrioxalate actinometry). The reaction produced stoichiometric amounts of chloride ion indicating complete dechlorination of the chlorinated n-alkane. T4C10 degraded very slowly under Fenton (Fe2+/H2O2/dark) and Fenton-like (Fe3+/H2O2/dark) conditions. However, when the same solutions were irradiated, T4C10 degraded more rapidly than in the H2O2/UV system, with 61% disappearance in 10 min of exposure. The rapid degradation is related to the enhanced degradation of hydrogen peroxide to oxidizing *OH radicals under photo-Fenton conditions. Degradation was inhibited in both the H2O2/UV and photo-Fenton systems by the addition of KI and tert-butyl alcohol due to *OH scavenging.     

Photooxidation of naphthalenesulfonic acids: comparison between processes based on O(3), O(3)/activated carbon and UV/H(2)O(2)

The aim of the present study was to analyze and compare the efficacy of UV photodegradation with that of different advanced oxidation processes (O(3), UV/H(2)O(2), O(3)/activated carbon) in the degradation of naphthalenesulfonic acids from aqueous solution and to investigate the kinetics and the mechanism involved in these processes. Results obtained showed that photodegradation with UV radiation (254 nm) of 1-naphthalenesulfonic, 1,5-naphthalendisulfonic and 1,3,6-naphthalentrisulfonic acids is not effective. Presence of duroquinone and 4-carboxybenzophenone during UV irradiation (308-410 nm) of the naphthalenesulfonic acids increased the photodegradation rate. Addition of H(2)O(2) during irradiation of naphthalenesulfonic acids accelerated their elimination, due to the generation of ()OH radicals in the medium. Comparison between UV photodegradation 254 m and the advanced oxidation processes (O(3), O(3)/activated carbon and UV/H(2)O(2)) showed the low-efficacy of the former in the degradation of these compounds from aqueous medium. Thus, among the systems studied, those based on the use of UV/H(2)O(2) and O(3)/activated carbon were the most effective in the oxidation of these contaminants from the medium. This is because of the high-reactivity of naphthalenesulfonic acids with the *OH radicals generated by these two systems. This was confirmed by the values of the reaction rate constant of *OH radicals with these compounds k(OH), obtained by competitive kinetics (5.7 x 10(9) M(-1) s(-1), 5.2 x 10(9) M(-1) s(-1) and 3.7 x 10(9) M(-1) s(-1) for NS, NDS and NTS, respectively).     

代谢表面活性剂菌处理含油污泥的研究

试验采用异位生物修复技术堆肥法,对某炼厂油泥进行生物修复处理研究.用微生物代谢的表面活性剂对油泥进行预处理,洗脱油泥中部分油分后进行堆肥试验,投加从油田含油土壤中获得的以石油为唯一碳源、代谢高效生物表面活性剂的微生物C-2菌、F-2菌以及无机营养物和疏松剂(锯末),降解油泥中的石油污染物.经过外源微生物和内源微生物共同作用120 d,油泥中的石油烃总量由22 910 mg/kg下降到3 000 mg/kg以下.试验利用色谱-质谱联用方法分析了降解前后石油组分的变化.菌株经传统方法鉴定为蜡状芽孢杆菌、枯草芽孢杆菌.     

Degradation of sodium 4-dodecylbenzenesulphonate photoinduced by Fe(III) in aqueous solution

The Fe(III)-photoinduced degradation of 4-dodecylbenzenesulphonate (DBS) in aqueous solution was investigated. The mixing of DBS (1 mm) and Fe(III) (1 mm) solutions immediately led to the formation of a precipitate that contained DBS and monomeric Fe(OH)2+, the predominant Fe(III) species. Both species were also present in the supernatant. Irradiation of the supernatant solution resulted in a photoredox process that yielded Fe(II) and *OH radicals. The disappearance of DBS was shown to involve only attack by *OH radicals; the quantum yield of DBS disappearance is similar to the quantum yield of *OH radical formation. A wavelength effect was also observed; the rate of DBS disappearance was higher for shorter wavelength irradiation. Five photoproducts, all containing the benzene sulphonate group, were identified. *OH radicals preferentially abstract hydrogen from the carbon in the alpha position of the aromatic ring. The results show that the Fe(III)-photoinduced degradation of DBS could be used as an alternative method for polluted water treatment.     

Contribution of free radicals to chlorophenols decomposition by several advanced oxidation processes

The chemical decomposition of aqueous solutions of various chlorophenols (4-chlorophenol (4-CP), 2,4-dichlorophenol (2-DCP), 2,4,6-trichlorophenol (2,4,6-TCP) and 2,3,4,6-tetrachlorophenol (2,3,4,6-TeCP)), which are environmental priority pollutants, is studied by means of single oxidants (hydrogen peroxide, UV radiation, Fenton's reagent and ozone at pH 2 and 9), and by the Advanced Oxidation Processes (AOPs) constituted by combinations of these oxidants (UV/H2O2 UV/Fenton's reagent and O3/UV). For all these reactions the degradation rates are evaluated by determining their first-order rate constants and the half-life times. Ozone is more reactive with higher substituted CPs while OH* radicals react faster with those chlorophenols having lower number of chlorine atoms. The improvement in the decomposition levels reached by the combined processes, due to the generation of the very reactive hydroxyl radicals. in relation to the single oxidants is clearly demonstrated and evaluated by kinetic modeling.     

Inactivation of Bacillus subtilis spores during ozonation in water treatment plant: influence of pre-treatment and consequences for positioning of the ozonation step

This study reports on quantitative methodology for rational selection of the ozone injection point within unit processes of conventional drinking water treatment plants to improve disinfection efficiencies. The method is based on the fact that a specific inactivation level of microorganisms is achieved at a unique value of ozone exposures, independent of ozone dose and type of water, and quantitatively described by a Delayed Chick-Watson model (C T(lag): 1.03mgl(-1), k: 1.44mg(-1)lmin(-1)). This study demonstrated this phenomenon by performing the inactivation of Bacillus subtilis (B. subtilis) spores with ozone in various types of water collected from a series of unit processes in a water treatment plant. Simple measurements of the ozone decomposition behavior in waters from each unit process of a water treatment plant can allow the quantitative evaluation of the ozone needed to achieve a required level of inactivation. This methodology will be useful for drinking water treatment plants which intend to improve the disinfection efficiencies of their ozonation process.     

3-Chlorophenol elimination upon excitation of dilute iron(III) solution: evidence for the only involvement of Fe(OH)2+

The transformation of 3-chlorophenol (3CP) photoinduced by iron(II) in aqueous solution has been investigated under monochromatic irradiation (lambda(exc) = 365 nm) representative of atmospheric solar emission. Hydroxyl radicals are formed via an intramolecular photoredox process in iron(III) excited hydroxy-complexes. Fe(OH)2+ is the most active complex in terms of HO* formation and according to our experiments and calculations, it appears that Fe(OH)2+ is the only iron(III) species involved in 3CP oxidation process. Hydroxyl radicals react very rapidly with 3CP, which is eliminated from the solution. The primary intermediates do not accumulate in the medium but rapidly degraded to non-absorbing compounds by a subsequent action of hydroxyl radicals.     

Removal of SO2 from simulated flue gases using non-thermal plasma-based microgap discharge

The removal of sulfur dioxide (SO2) from simulated flue gases streams (N2/O2/H2O/SO2) was experimentally investigated using microgap discharge. In the experiment, the thinner dielectric layers of aluminum oxide (Al2O3) were used to form the microgap discharge. With this physical method, a high concentration of hydroxyl (OH*) radicals were produced using the ionization of O2 and H2O to further the conversion of SO2 into sulfuric acid (H2SO4) at 120 degrees C in the absence of any catalysts and absorbents, which were captured with the electrostatic precipitator (ESP). As a result, the increase of discharge power and concentrations of O2 and H2O increased the production of OH. radicals resulting in enhanced removal of SO2 from gas streams. With the test and analysis, a number of H2SO4 droplets were produced in experiment. Therefore, a new method for removal of SO2 in semidry method without ammonia (NH3) additive was found.     

水质净化高效复合微生态制剂的研制

在室内模拟条件下,采用正交实验的方法对光合细菌、枯草芽孢杆菌和反硝化细菌的复配比例进行了研究,筛选一种用于水产养殖水质净化的高效复合微生态制剂。结果表明,当光合细菌(菌细胞浓度约为2×109CFU/mL)、枯草芽孢杆菌(菌细胞浓度约为8×108CFU/mL)和反硝化细菌(菌细胞浓度约为8×108CFU/mL)按菌液体积比为1∶2∶1进行复配利于水中溶解氧的提高和COD、氨氮、亚硝态氮、硝态氮的降解。验证实验表明,筛选组合各指标均优于商品微生态制剂和空白对照,其中溶解氧含量显著高于商品微生态制剂EM和复合芽孢菌处理,在实验第5天对COD的降解率为95%,显著优于EM和复合芽孢菌处理的66.3%和47.9%,实验第7天对氨氮、亚硝态氮和硝态氮的降解率分别达到70%、89%和56%。     

Kinetics of oxidation of chlorobenzenes and phenyl-ureas by Fe(II)/H2O2 and Fe(III)/H2O2. Evidence of reduction and oxidation reactions of intermediates by Fe(II) or Fe(III)

The rates of degradation of 1,2,4-trichlorobenzene (TCB), 2,5-dichloronitrobenzene (DCNB), diuron and isoproturon by Fe(II)/H2O2 and Fe(III)/H2O2 have been investigated in dilute aqueous solution ([Organic compound]0 approximately 1 microM, at 25.0 +/- 0.2 degrees C and pH < or = 3). Using the relative rate method with atrazine as the reference compound, and the Fe(II)/H2O2 (with an excess of Fe(II)) and Fe(III)/H2O2 systems as sources of OH radicals, the rate constants for the reaction of OH* with TCB and DCNB were determined as (6.0 +/- 0.3)10(9) and (1.1 +/- 0.2)10(9) M(-1) s(-1). Relative rates of degradation of diuron and isoproturon by Fe(II)/H2O2 were about two times smaller in the absence of dissolved oxygen than in the presence of oxygen. These data indicate that radical intermediates are reduced back to the parent compound by Fe(II) in the absence of oxygen. Oxidation experiments with Fe(III)/H2O2 showed that the rate of decomposition of atrazine markedly increased in the presence of TCB and this increase has been attributed to a regeneration of Fe(II) by oxidation reactions of intermediates (radical species and dihydroxybenzenes) by Fe(III).     

Temperature dependence of hydroxyl radical formation in the hv/Fe3+/H2O2 and Fe3+/H2O2 systems

The thermal enhancement of the formation of *OH by the hv/Fe(III)/H2O2 system (including the Fe(III)/H2O2 system) was quantitatively investigated with reaction temperatures ranging from 25 to 50 degrees C. A temperature dependent kinetic model for the hv/Fe(III)/H2O2 system, incorporating 12 major reactions with no fitted rate constants or activation energies, was developed, and successfully explained the experimental measurements. Particularly, the thermal enhancement of Fe(OH)2+ photolysis which is the most significant step in the hv/Fe(III)/H2O2 system was effectively explained by two factors; (1) the variation of the Fe(OH)2+ concentration with temperature, and (2) the temperature dependence of the quantum yield for Fe(OH)2+ photolysis (measured activation energy=11.4 kJ mol(-1)). Although in both the hv/Fe(III)/H2O2 and Fe(III)/H2O2 systems, elevated temperatures enhanced the formation of *OH, the thermal enhancement was much higher in the dark Fe(III)/H2O2 system than the hv/Fe(III)/H2O2 system. Furthermore, it was found that the relative thermal enhancement of the formation of *OH in the presence of *OH scavengers (tert-butyl alcohol) was magnified in the Fe(III)/H2O2 system but was not in the hv/Fe(III)/H2O2 system.     

Fe(III)-solar light induced degradation of diethyl phthalate (DEP) in aqueous solutions

The degradation of diethyl phthalate (DEP) photoinduced by Fe(III) in aqueous solutions has been investigated under solar irradiation in the compound parabolic collector reactor at Plataforma Solar de Almeria. Hydroxyl radicals *OH, responsible of the degradation, are formed via an intramolecular photoredox process in the excited state of Fe(III) aquacomplexes. The primary step of the reaction is mainly due to the attack of *OH radicals on the aromatic ring. For prolonged irradiations DEP and its photoproducts are completely mineralized due to the regeneration of the absorbing species and the continuous formation of *OH radicals that confers a catalytic aspect to the process. Consequently, the degradation photoinduced by Fe(III) could be an efficient method of DEP removal from water.     

Effects of freezing on the survival of Escherichia coli and Bacillus and response to UV and chlorine after freezing.

Escherichia coli (E. coli) and Bacillus megaterium bacteria were frozen at -15 degrees C using a freezer and a spray freezing method. The frozen Bacillus spores were also exposed to UV and free chlorine. An average of 4.7-log inactivation was obtained from the spray ice with 2-day storage time, while the freezer freezing only caused 0.84-log reduction with the same storage time. Significantly higher inactivation levels were observed for the E. coli cells with 2-day storage compared with those without storage. The spray freezing was found more effective in killing the E. coli cells, while more cells were sublethally injured by the freezer freezing. Freezing did not kill the Bacillus megaterium spores, but affected their response to UV and chlorine. Greater inactivation levels were observed at higher free chlorine doses or longer contact time, and the UV fluence-response curve showed initial rapid kill followed by tailing for the frozen spores.     

Photo-induced degradation of diuron in aqueous solution by nitrites and nitrates: kinetics and pathways

The photo-induced degradation of diuron (3-(3,4-dichlorophenyl)-1,1-dimethylurea) in aqueous solution under simulated solar irradiation has been investigated in the presence of NO3-/NO2- ions. The degradation rates were compared by varying environmental parameters including substrate and inducer concentrations, oxygen content and pH. The photoproducts were identified by extensive LC-ESI-MS and LC-ESI-MS-MS studies after SPE preconcentration on prepacked cartridges. In both NO3- and NO2- conditions, oxidation of the N-(CH3)2 terminus group is the main process leading to the N-monodemethylated (NHCH3), N-formyl (N(CH3)CHO) and the uncommon and unstable carbinolamine (N(CH3)CH2OH) by-products. Cl/OH substituted and nitrated phenylureas are formed minorily. Degradation pathways involving OH* and NO2* (or dimer) radicals as reactive species are proposed.     

Comparison of the degradation of p-hydroxybenzoic acid in aqueous solution by several oxidation processes

A comparative study is made of 12 methods of chemical oxidation applied to degrading p-hydroxybenzoic acid in aqueous solution. The oxidation processes tested were: UV, O3, UV/TiO2, O3/Fe2+, O3/H2O2, O3/UV, UV/H2O2, H2O2/Fe2+, H2O2/Fe2+/O3, UV/H2O2/O3, H2O2/Fe2+/UV and O3/UV/H2O2/Fe2+. The 12 processes were ranked by reactivity. In a kinetic study, the overall kinetic rate constant was split up into three components: direct oxidation by UV irradiation (photolysis), direct oxidation by ozone (ozonation), and oxidation by free radicals (mainly OH*).     

Kinetics of quinoline degradation by O3/UV in aqueous phase

The kinetics of quinoline degradation by O3/UV in aqueous phase was studied in this paper. It was found that the stoichiometric factor for the number of ozone molecule consumed by per quinoline molecule was 1. The second-order rate constants at 15 degrees C for the direct reaction of quinoline with ozone and that for the reaction of quinoline with *OH were determined to be 51.0 and 7.24 x 10(9) M(-1)s(-1), respectively. In O3/UV reaction system, *OH was the more important oxidant to degrade quinoline than ozone. For a comparison, in O3 reaction system, the relative importance of the two oxidants depended on the pH value greatly. To make the degradation of quinoline more practical, improvement of the concentration of *OH is more feasible.     

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.     

Oxidative degradation of dimethylsulfoxide by locally concentrated hydroxyl radicals in streamer corona discharge process

This study systematically investigates the characteristic degradation behaviors of dimethylsulfoxide (DMSO) by the streamer corona discharge process (SCDP) in water. The analysis of the oxidized intermediates of DMSO shows that hydroxyl radical (*OH) is the main oxidant responsible for the degradation of DMSO in the SCDP. The various experiments on the degradation and mineralization of DMSO, and the effect of the *OH scavenger suggest that the SCDP produces locally concentrated *OHs in and around the plasma channel. This explanation was also supported by the formation of H(2)O(2) and the effect of the *OH scavenger on the H(2)O(2) production rate in the SCDP. Based on the kinetic data for the degradation of DMSO and the production of H(2)O(2) in the SCDP, the volume of the active region in which the *OHs are concentrated, and the effective concentration of *OH in that region were estimated to be 0.21 microl and 5.0 x 10(-3)M, respectively. This level of *OH concentration in the SCDP is approximately 10(7)-10(9) times higher than that generated in ordinary advanced oxidation processes using *OH. The ramifications of the results obtained in this study on successful water treatment using the SCDP are also discussed.