Para-chlorophenol containing synthetic wastewater treatment in an activated sludge unit: effects of hydraulic residence time

Due to the toxic nature of chlorophenol compounds present in some chemical industry effluents, biological treatment of such wastewaters is usually realized with low treatment efficiencies. Para-chlorophenol (4-chlorophenol, 4-CP) containing synthetic wastewater was treated in an activated sludge unit at different hydraulic residence times (HRT) varying between 5 and 30 h while the feed COD (2500 mg l(-1)), 4-CP (500 mg l(-1)) and sludge age (SRT, 10 days) were constant. Effects of HRT variations on COD, 4-CP, toxicity removals and on settling characteristics of the sludge were investigated. Percent COD removals increased and the effluent COD concentrations decreased when HRT increased from 5 to 15 h and remained almost constant for larger HRT levels. Nearly, 91% COD and 99% 4-CP removals were obtained at HRT levels above 15 h. Because of the highly concentrated microbial population at HRT levels of above 15 h, low effluent (reactor) 4-CP concentrations and almost complete toxicity removals were obtained. High biomass concentrations obtained at HRT levels above 15 h were due to low 4-CP contents in the aeration tank yielding negligible inhibition effects and low maintenance requirements. The sludge volume index (SVI) decreased with increasing HRT up to 15 h due to high biomass concentrations at high HRT levels resulting in well settling sludge with low SVI values. Hydraulic residence times above 15 h resulted in more than 90% COD and complete 4-CP and toxicity removals along with well settling sludge.     

Effect of feeding time on the performance of a sequencing batch reactor treating a mixture of 4-CP and 2,4-DCP

This paper investigated the biodegradation kinetics of 4-chlorophenol (4-CP) and 2,4-dichlorophenol (2,4-DCP) separately in batch reactors and mixed in sequencing batch reactors (SBRs). Batch reactor experiments showed that both 4-CP and 2,4-DCP began to inhibit their own degradation at 53 and 25 mg l(-1), respectively, and that the Haldane equation gave a good fit to the experimental data because r(2) values were higher than 0.98. The maximum specific degradation rates (q(m)) were 130.3 and 112.4 mg g(-1) h for 4-CP and 2,4-DCP, respectively. The values of the half saturation (K(s)) and self-inhibition constants (K(i)) were 34.98 and 79.74 mg l(-1) for 4-CP, and 13.77 and 44.46 mg l(-1) for 2,4-DCP, respectively. The SBR was fed with a mixture of 220 mg l(-1) of 4-CP, 110 mg l(-1) of 2,4-DCP, and 300 mg l(-1) of peptone as biogenic substrate at varying feeding periods (0-8h) to evaluate the effect of feeding time on the performance of the SBR. During SBR operation, in addition to self-inhibition, 4-CP degradation was strongly and competitively inhibited by 2,4-DCP. The inhibitory effects were particularly pronounced during short feeding periods because of higher chlorophenol peak concentrations in the reactor. The competitive inhibition constant (K(ii)) of 2,4-DCP on 4-CP degradation was 0.17 mg l(-1) when the reactor was fed instantaneously (0 h feeding). During longer feedings, increased removal/loading rates led to lower chlorophenol peak concentrations at the end of feeding. Therefore, in multi-substrate systems feeding time plus reaction time should be determined based on both degradation kinetics and substrate interaction. During degradation, the meta cleavage of 4-chlorocatechol resulted in accumulation of a yellowish color because of the formation of 5-chloro-2-hydroxymuconic semialdehyde (CHMS), which was further metabolized. Isolation and enrichment of the chlorophenols-degrading culture suggested Pseudomonas sp. and Pseudomonas stutzeri to be the dominant species.     

Toxicity of ozonated animal manure to the house fly, Musca domestica

Swine manure slurries were ozonated at a dosage of 1 g/L and tested for their toxicity to the house fly (Musca domestica). The observed toxicity of ozonated swine manure was consistent and independent of origin of the swine manure. A dose (dilution) response curve was performed. A 50% dilution in the ozonated swine manure slurry resulted in 90% reduction in toxicity. Neither the synthetic nor ozonated synthetic swine manure, both of which contained higher concentrations of formaldehyde and three other unidentified carbonyl compounds than the ozonated swine manure, were toxic to the flies. Ozonated swine manure slurry was centrifuged and passed through a 0.45-microm filter. The liquid phase was as toxic as the unfiltered slurry; as such, the toxicant appears to be present in liquid phase. Neither ammonia, hydrogen sulfide, formaldehyde, nor other simple aldehydes appeared to be the toxic agent. The toxic agent appears to be a polar chemical compound and is concentrated in the urine. Several possible compounds have been identified. The toxicity of untreated and ozonated manure slurries from different livestock was compared. Six animal manure slurries (beef and dairy cattle, horse, poultry, sheep, and swine) were ozonated (dosage of 1 g/L) and tested for toxicity to the house fly. Ozonated dairy cattle manure slurry showed 78% mortality after 72 h, whereas ozonated swine manure slurry achieved a 100% mortality rate in 48 h. Neither the unozonated dairy nor swine manure slurries, nor any of the other raw or ozonated manure slurries, were toxic to the flies.     

Combined chemical and biological oxidation of penicillin formulation effluent

Antibiotic formulation effluent is well known for its important contribution to environmental pollution due to its fluctuating and recalcitrant nature. In the present study, the chemical treatability of penicillin formulation effluent (average filtered COD(o)=830 mg/l; average soluble COD(o)=615 mg/l; pH(o)=6.9) bearing the active substances penicillin Amoxicillin Trihydrate (C(16)H(19)N(3)O(5)S.3H(2)O) and the beta-lactamase inhibitor Potassium Clavulanate (C(8)H(8)KNO(5)) has been investigated. For this purpose, the penicillin formulation effluent was subjected to ozonation (applied ozone dose=2500 mg/(lxh)) at varying pH (2.5-12.0) and O(3)+H(2)O(2) (perozonation) at different initial H(2)O(2) concentrations (=2-40 mM) and pH 10.5. According to the experimental results, the overall Chemical Oxygen Demand (COD) removal efficiency varied between 10 and 56% for ozonation and 30% (no H(2)O(2)) and 83% (20 mM H(2)O(2)) for the O(3)+H(2)O(2) process. The addition of H(2)O(2) improved the COD removal rates considerably even at the lowest studied H(2)O(2) concentration. An optimum H(2)O(2) concentration of 20 mM existed at which the highest COD removal efficiency and abatement kinetics were obtained. The ozone absorption rate ranged between 53% (ozonation) and 68% (perozonation). An ozone input of 800 mg/l in 20 min was sufficient to achieve the highest BOD(5)/COD (biodegradability) ratio (=0.45) and BOD(5) value (109 mg/l) for the pre-treated penicillin formulation effluent. After the establishment of optimum ozonation and perozonation conditions, mixtures of synthetic domestic wastewater+raw, ozonated and perozonated penicillin formulation effluent were subjected to biological activated sludge treatment at a food-to-microorganisms (F/M) ratio of 0.23 mg COD/(mg MLSSxd), using a consortium of acclimated microorganisms. COD removal efficiencies of the activated sludge process were 71, 81 and 72% for pharmaceutical wastewater containing synthetic domestic wastewater mixed with either raw, ozonated or perozonated formulation effluent, respectively. The ultimate COD value obtained after 24-h biotreatment of the synthetic domestic wastewater+pre-ozonated formulation effluent mixture was around 100 mg/l instead of 180 mg/l which was the final COD obtained for the wastewater mixture containing raw formulation effluent, indicating that pre-ozonation at least partially removed the non-biodegradable COD fraction of the formulation effluent.     

剩余污泥经臭氧破解后其中碳、氮和磷的变化

在臭氧对污泥进行减量的过程中,针对臭氧作用后污泥中碳、氮和磷数量的变化,对污水处理厂的剩余污泥进行了不同累计时间的臭氧作用研究,结果表明经臭氧破解后污泥中的TN没有较大改变,污泥中的TP最终呈减少趋势,破解液中的COD虽有所增加,但破解液回流到生物系统中反而可以补充反硝化过程中有机碳的不足,从而促进污水生物处理的脱氮除磷作用,臭氧的引入不仅可以减少污水处理厂的运行成本,同时可为城镇污水处理厂全面升级改造提供一定的参考。     

Preparation of novel activated carbons from H2SO4-pretreated corncob hulls with KOH activation for quick adsorption of dye and 4-chlorophenol

Corncob hull was immersed in 25 wt% H(2)SO(4) and was carbonized in an oven at 290 °C for 2h to obtain the char. The char was then activated for 1h at 780 °C by KOH at weight ratio of KOH/char of 2.5, 3.0, and 3.5. SEM photos of the carbons revealed that the cell wall of corncob hull was etched into thin film structure. It was shown that the adsorption isotherms of methylene blue and 4-chlorophenol on the carbons were well fitted by the Langmuir equation. Moreover, the adsorption kinetics could be satisfactorily described by the Elovich equation. The normalized standard deviations are less than 2.8%. The high fraction of adsorption amount adsorbed within 1 min to that at saturation demonstrated the advantage of the prepared activated carbons. The fraction of adsorption amount within 1 min to that at saturation (q(1)/q(mon)) for the adsorption of 4-CP is high up to 0.807. Such quick adsorption behavior was mainly attributed to the presence of the thin film structure of carbons.     

Oxidation and detoxification of pentachlorophenol in aqueous phase by ozonation

The degradation and detoxification performance of ozonation in treating pentachlorophenol (PCP) contaminated wastewater was determined. All experiments were conducted in a bench scale glass column equipped with ceramic diffuser and a lab-scale ozone generator under ambient temperature and pH 7. The decomposition rate of PCP in this study was primarily controlled by the ozone mass transfer rate from gas to liquid phases. Principal intermediates found were 2,3,4,6- and 2,3,5,6-tetrachlorophenols (TeCP) and phenol. PCP seems to be more vulnerable to ozone than its intermediates. A bioluminescence technique was used to evaluate the toxicity of PCP with Vibrio fisheri NRRL B-11177 as the test bacterium, and the EC(50) of PCP was found to be 1.0 mg l(-1). Detoxification occurred as the PCP and TeCP reacted with ozone and decomposed to less chlorinated congeners and phenol.     

铁元素对有机物厌氧降解的影响研究

不同价态的铁元素氧化还原性不同,对有机物的厌氧生物降解过程的影响也不同。以邻氟苯酚和硝基苯为目标污染物,投铁量为20～100mg／L的条件下,单质铁能加速硝基苯的厌氧降解,对2-氟酚降解的影响则很小;二价铁和三价铁对两种物质都表现出一定的抑制作用,投加浓度越高,抑制作用越明显。     

Degradation of a commercial textile biocide with advanced oxidation processes and ozone

The occurrence of significant amounts of biocidal finishing agents in the environment as a consequence of intensive textile finishing activities has become a subject of major public health concern and scientific interest only recently. In the present study, the treatment efficiency of selected, well-known advanced oxidation processes (Fenton, Photo-Fenton, TiO(2)/UV-A, TiO(2)/UV-A/H(2)O(2)) and ozone was compared for the degradation and detoxification of a commercial textile biocide formulation containing a 2,4,4'-trichloro-2'-hydroxydiphenyl ether as the active ingredient. The aqueous biocide solution was prepared to mimic typical effluent originating from the antimicrobial finishing operation (BOD(5,o) < or =5 mg/L; COD(o)=200 mg/L; DOC(o) (dissolved organic carbon)=58 mg/L; AOX(o) (adsorbable organic halogens)=48 mg/L; LC(50,o) (lethal concentration causing 50% death or immobilization in Daphnia magna)=8% v/v). Ozonation experiments were conducted at different ozone doses (500-900 mg/h) and initial pH (7-12) to assess the effect of ozonation on degradation (COD, DOC removal), dearomatization (UV(280) and UV(254) abatement), dechlorination (AOX removal) and detoxification (changes in LC(50)). For the Fenton experiments, the effect of varying ferrous iron catalyst concentrations and UV-A light irradiation (the Photo-Fenton process) was examined. In the heterogenous photocatalytic experiments, Degussa P25-type TiO(2) was used as the catalyst and the effect of reaction pH (3, 7 and 12) and H(2)O(2) addition on the photocatalytic treatment efficiency was examined. Although in the photochemical (i.e. Photo-Fenton, TiO(2)/UV-A and TiO(2)/UV-A/H(2)O(2)) experiments appreciably higher COD and DOC removal efficiencies were obtained, ozonation appeared to be equally effective to achieve dearomatization (UV(280) abatement) at all studied reaction pH. During ozonation of the textile biocide effluent, AOX abatement proceeded significantly faster than dearomatization and was complete after 20 min ozonation (267 mg O(3)). On the other hand, for complete detoxification, ozonation had to be continued for at least 30 min (corresponding to 400mg O(3)). Effective AOX and acute toxicity removal was also obtained after heterogeneous photocatalytic treatment (TiO(2)/UV-A and TiO(2)/UV-A/H(2)O(2)). The Fenton-based treatment experiments and particularly the dark Fenton reaction resulted in relatively poor degradation, dearomatization, AOX and acute toxicity removals.     

Kinetic studies on the adsorption of phenol, 4-chlorophenol,and 2,4-dichlorophenol from water using activated carbons

This study uses rate parameters in pseudo-first-order (PFO) and pseudo-second-order (PSO) equations (k₁ and k₂q_e, respectively) to judge the extent for approaching equilibrium in an adsorption process. Out of fifty-six systems collected from the literature, the adsorption processes with a k₂q_e value between 0.1 and 0.8 min^?1 account for as much as 70% of the total. These are classified as fast processes. This work compares the validity of PFO and PSO equations for the adsorption of phenol, 4-chlorophenol (4-CP), and 2,4-dichlorophenol (2,4-DCP) on activated carbons prepared from pistachio shells at different NaOH/char ratios. The activated carbons, recognized as microporous materials, had a surface area ranging from 939 to 1936 m²/g. Findings show that the adsorption of phenol, 4-CP, and 2,4-DCP on activated carbons had a k₂q_e value of 0.15–0.58 min^?1, reflecting the fast process. Evaluating the operating time by rate parameters revealed that k₂q_e was 1.6–1.8 times larger than k₁. These findings demonstrate the significance of using an appropriate kinetic equation for adsorption process design.     

ACUTE RESIDUAL TOXICITY OF SEVERAL WASTEWATER DISINFECTANTS TO AQUATIC LIFE1

ABSTRACT: This study was conducted to determine the comparative acute toxicity of chlorine, bromine chloride and ozone in wastewater, and to determine any acute toxicity associated with chlorinated wastewater which had been dechlorinated with sulfur dioxide. Toxicity tests were conducted with several species of cyprinids, salmonids and centrarchids, and the freshwater macroinvertebrate, Daphnia magna. Chlorinated effluent exhibited the greatest potential for residual toxicity of any disinfected stream tested. The reduced residual toxicity of chlorobrominated or ozonated effluent was largely the result of the more rapid dissipation of these disinfectants in wastewater. The acute residual toxicity of chlorinated effluent was eliminated by dechlorination with sulfur dioxide.     

Merits of ozonation and catalytic ozonation pre-treatment in the algal treatment of pulp and paper mill effluents

Since the performance of algal treatment for pulp mill effluent decreases with increasing color intensity and AOX content, which mainly originate from the chlorine bleaching of Kraft pulp, the separated CEH bleaching effluent was pre-treated by both the conventional and the heterogeneous catalytic ozonation processes. An increase in the BOD(5)/COD ratio from 0.11 to 0.28 and 87% color abatement in terms of Pt-Co were achieved by catalytic ozonation, which had the best treatment performance. Biodegradability enhancement of the CEH effluent correlated well with a decrease in toxicity, high-molecular-weight-compound content, and AOX abatement. By the pre-treatment of the CEH bleaching effluent, the overall efficiencies of algal treatment of the combined pulp mill effluent in terms of the fractional removal of COD and color were increased from 76% and 53% to 86-90% and 96-99%, respectively. Effects of both the conventional and the catalytic ozonation pre-treatments on subsequent biological treatment were close to each other and they reduced the filling period of the Sequential Batch Reactor (SBR) cycle from 8 to 5 days.     

Preparation of activated carbons from unburnt coal in bottom ash with KOH activation for liquid-phase adsorption

In this work, unburnt coal (UC) in bottom ash from coal-fired power plants was soaked in KOH solution and activated for 1 h at 780 °C. The yield of activated carbons varied from 47.8 to 54.8% when the KOH/UC weight ratio changed from 2 to 4. Pore properties of these activated carbons including the BET surface area, pore volume, pore size distribution, and pore diameter were characterized based on N₂ adsorption isotherms. It was shown that the isotherms for the adsorption of methylene blue, acid blue 74, and 4-chlorophenol from aqueous solutions on these activated carbons at 30 °C were well fitted by the Langmuir equation (correlation coefficient r² > 0.9968). The adsorption capacities of methylene blue, acid blue 74, and 4-chlorophenol were obtained to be 2.40–2.88, 0.57–1.29, and 2.34–5.62 mmol/g, respectively. Moreover, the adsorption kinetics could be suitably described by the Elovich equation.     

Photocatalytic activity of tungsten-doped TiO2 with hydrothermal treatment under blue light irradiation

Tungsten doping and hydrothermal treatment were found to significantly improve the visible-light photoactivity of TiO(2) synthesized by the sol-gel method. It was observed that TiO(2) doped with a 0.5% W:Ti mole ratio and treated with 4 h of hydrothermal curing showed photoactivity under blue light irradiation equal to 74% of the commercial Degussa P-25 under UV irradiation, i.e., 0.01 mM 2-chlorophenol was completely removed in 120 and 90 min, respectively. Light absorptivity and photocatalytic activity under blue light irradiation were not dependent on the crystallite structure of the TiO(2). The oxidation kinetics under blue light irradiation can be effectively explained by the Langmuir-Hinshelwood model with an apparent reaction rate constant and a Langmuir constant of 3.60 × 10(-4) mM min(-1) and 206.53 mM(-1), respectively.     

Winsor I微乳液+臭氧氧化联合处理油基岩屑的研究

采用“含有配制油基钻井液用主乳和油相的Winsor I微乳液+臭氧氧化”联合工艺对油基岩屑进行处理,Winsor I微乳液处理油基岩屑后的所得基础油和部分主乳进入平衡油相,可以用来配制油基钻井液,臭氧氧化对岩屑进行深度处理,进一步降低岩屑表面含油量。论文以处理后岩屑含油量为指标,系统优化了微乳液组成、微乳液清洗油基岩屑工艺和臭氧氧化工艺。实验结果建议微乳液组成为“脂肪醇聚氧乙烯醚硫酸钠+配制油基钻井液用主乳(2:1)”混合乳化剂浓度为6wt%,正戊醇浓度5 wt%,柴油浓度36 wt%,其他为盐水。推荐微乳液清洗条件为固液比1:5,室温下搅拌清洗60 min。此条件下岩屑含油量可以降低至1.41 wt%,微乳液重复使用4次后,岩屑含油量仍可以保持在2.0 wt%以下。臭氧氧化深度处理时,建议工艺条件为臭氧氧化时间40 min,清水pH=7,固液比1:5,臭氧流量5 mg/min,处理后岩屑含油量可降低至0.36wt%。     

The impact of alum addition on organic P transformations in poultry litter and litter-amended soil

Poultry litter treatment with alum (Al(2)(SO(4))(3) . 18H(2)O) lowers litter phosphorus (P) solubility and therefore can lower litter P release to runoff after land application. Lower P solubility in litter is generally attributed to aluminum-phosphate complex formation. However, recent studies suggest that alum additions to poultry litter may influence organic P mineralization. Therefore, alum-treated and untreated litters were incubated for 93 d to assess organic P transformations during simulated storage. A 62-d soil incubation was also conducted to determine the fate of incorporated litter organic P, which included alum-treated litter, untreated litter, KH(2)PO(4) applied at 60 mg P kg(-1) of soil, and an unamended control. Liquid-state (31)P nuclear magnetic resonance indicated that phytic acid was the only organic P compound present, accounting for 50 and 45% of the total P in untreated and alum-treated litters, respectively, before incubation and declined to 9 and 37% after 93 d of storage-simulating incubation. Sequential fractionation of litters showed that alum addition to litter transformed 30% of the organic P from the 1.0 mol L(-1) HCl to the 0.1 mol L(-1) NaOH extractable fraction and that both organic P fractions were more persistent in alum-treated litter compared with untreated litter. The soil incubation revealed that 0.1 mol L(-1) NaOH-extractable organic P was more recalcitrant after mixing than was the 1.0 mol L(-1) HCl-extractable organic P. Thus, adding alum to litter inhibits organic P mineralization during storage and promotes the formation of alkaline extractable organic P that sustains lower P solubility in the soil environment.     

Metabolic pathway of anaerobic digestion and reaction rate limiting step of 2,4,5-TCP

A study of the effluent of an anaerobic fluidized bed reactor acclimated to 2,4,5-TCP was made in order to determine the metabolic pathway and reaction rate limiting step of 2,4,5-TCP. The wastewater with about 2500 mg L⁻¹ COD and 50 mg L⁻¹ 2,4,5-TCP was biodegraded by anaerobic digestion, and the intermediate analyzed by HPLC and GC/MS. The results showed the degradative metabolic pathway of 2,4,5-TCP, under anaerobic conditions, to be: 2,4,5-TCP→3,4-DCP→3-CP→phenol→benzoate. For the rate limiting step, the accumulated concentration of 3,4-DCP was higher than other intermediates for Anaerobic Toxicity Assay (ATA) and Biochemical Methane Potential (BMP) tests. From the anaerobic fluidized bed reactor, analyses showed the chloride at the ortho-position was removed very quickly after 2,4,5-TCP entered the reactor. As for the intermediate products, 43% of 3,4-DCP was not decomposed and of the 3-CP only 6.4% left. This shows that the rate limiting step of 2,4,5-TCP was the dechlorination of 3,4-DCP.     

城市污水厂混合污泥好氧消化处理研究

以城市污水处理厂的初沉污泥与剩余污泥的混合污泥为对象,研究了影响污泥好氧消化处理的各项因素.通过测定氧摄取速率(OUR)和此污泥好氧速率(SOUR),对实验结果进行了探讨.     

混凝—催化臭氧化处理垃圾渗滤液MBR出水

本文研究了混凝—催化臭氧化对垃圾渗滤液MBR出水COD、UV254和色度的去除效果及可生化性能的影响。在pH 11,FeCl3用量800 mg/L的优化条件下,COD、UV254和色度去除率分别为37.8%、61.9%和88.7%。混凝出水催化臭氧化结果表明,3%-Ce/AC催化臭氧化效率最好,COD去除率为33.6%,臭氧消耗系数为1.40 mgO3/mgCOD。经混凝—催化臭氧化处理后,MBR出水的COD、UV254及色度总去除率分别为58.7%、90.8%及98.7%,BOD5/COD从0.036提高到0.375,可生化性明显改善。     

Characteristics of major secondary ions in typical polluted atmospheric aerosols during autumn in central Taiwan

In autumn of 2008, the chemical characteristics of major secondary ionic aerosols at a suburban site in central Taiwan were measured during an annually occurring season of high pollution. The semicontinuous measurement system measured major soluble inorganic species, including NH(4)(+), NO(3)(-), and SO(4)(2-), in PM(10) with a 15 min resolution time. The atmospheric conditions, except for the influences of typhoons, were dominated by the local sea-land breeze with clear diurnal variations of meteorological parameters and air pollutant concentrations. To evaluate secondary aerosol formation at different ozone levels, daily ozone maximum concentration (O(3,daily max)) was used as an index of photochemical activity for dividing between the heavily polluted period (O(3,daily max) ≧80 ppb) and the lightly polluted period (O(3,daily max)<80 ppb). The concentrations of PM(10), NO(3)(-), SO(4)(2-), NH(4)(+) and total major ions during the heavily polluted period were 1.6, 1.9, 2.4, 2.7 and 2.3 times the concentrations during the lightly polluted period, respectively. Results showed that the daily maximum concentrations of PM(10) occurred around midnight and the daily maximum ozone concentration occurred during daytime. The average concentration of SO(2) was higher during daytime, which could be explained by the transportation of coastal industry emissions to the sampling site. In contrast, the high concentration of NO(2) at night was due to the land breeze flow that transport inland urban air masses toward this site. The simulations of breeze circulations and transitions were reflected in transports and distributions of these pollutants. During heavily polluted periods, NO(3)(-) and NH(4)(+) showed a clear diurnal variations with lower concentrations after midday, possibly due to the thermal volatilization of NH(4)NO(3) during daytime and transport of inland urban plume at night. The diurnal variation of PM(10) showed the similar pattern to that of NO(3)(-) and NH(4)(+) aerosols. This indicated that the formatted secondary aerosols in the inland urban area could be transported to the coastal area by the weak land breeze and deteriorated the air quality in the coastal area at night.