Treatment of distillery spent-wash by ozonation and biodegradation: significance of pH reduction and inorganic carbon removal before ozonation.

This study is aimed at exploring strategies for mineralization of refractory compounds in distillery effluent by anaerobic biodegradation/ozonation/aerobic biodegradation. Treatment of distillery spent-wash used in this research by anaerobic-aerobic biodegradation resulted in overall COD removal of 70.8%. Ozonation of the anaerobically treated distillery spent-wash was carried out as-is (phase I experiments) and after pH reduction and removal of inorganic carbon (phase II experiments). Introduction of the ozonation step resulted in an increase in overall chemical oxygen demand (COD) removal, with the highest COD removals of greater than 95% obtained when an ozone dose of approximately 5.3 mg ozone absorbed/mg initial total organic carbon was used. The COD removal during phase II experiments was slightly superior compared with phase I experiments at similar ozone doses. Moreover, efficiency of ozone absorption from the gas phase into distillery spent-wash aliquots was considerably enhanced during phase II experiments.     

Enhancement of chemical-oxygen demand and color removal of distillery spent-wash by ozonation.

Distillery spent-wash has very high organic content (75,000 to 125,000 mg/L chemical-oxygen demand [COD]), color, and contains difficult-to-biodegrade organic compounds. For example, anaerobic treatment of the distillery spent-wash used in this study resulted in 60% COD reduction and low color removal. Subsequent aerobic treatment of the anaerobic effluent resulted in enhancement of COD removal to 66%. In this paper, the effect of ozonation on various properties of the anaerobically treated distillery effluent, including the effect on its subsequent aerobic biodegradation, was investigated. Ozonation of the anaerobically treated distillery effluent at various ozone doses resulted in the reduction of total-organic carbon (TOC), COD, COD/TOC ratio, absorbance, color, and increase in the biochemical-oxygen demand (BOD)/COD ratio of the effluent. Further, ozonation of the anaerobically treated distillery effluent at an ozone dose of 2.08 mg/mg initial TOC and subsequent aerobic biodegradation resulted in 87.4% COD removal, as compared to 66% removal when ozonation was not used.     

臭氧氧化法深度处理生活垃圾焚烧厂沥滤液

采用臭氧氧化法对生活垃圾焚烧厂沥滤液经生化处理后的废水(称沥滤液生化处理水)进行深度处理。实验结果表明,COD降解速率随废水pH的提高明显增加,其中pH=10.5时的COD降解速率常数约为pH=4时的5.8倍。在臭氧投量为52.92 mg/min、pH=10.5的条件下反应70 min后,UV254和COD去除率分别达到84.7%和59.3%。向反应体系投加叔丁醇后COD去除率下降了约15%,由羟自由基氧化去除的COD占总COD去除量的26.7%。毒性实验结果表明,沥滤液生化处理水的96 h-EC50为38%,经臭氧氧化进一步处理后出水的96 h-EC50为77%,表明经臭氧深度处理后沥滤液生化处理水的毒性明显降低。     

Ozonation of oxytetracycline and toxicological assessment of its oxidation by-products

Antibiotic formulation effluents are well known for their difficult elimination by traditional bio-treatment methods and their important contribution to environmental pollution due to its fluctuating and recalcitrant nature. In the present study the effect of ozonation on the degradation of oxytetracycline (OTC) aqueous solution (100mgl(-1)) at different pH values (3, 7 and 11) was investigated. Ozone (11mgl(-1) corresponds the concentration of ozone in gas phase) was chosen considering its rapid reaction and decomposition rate. The concentration of oxytetracycline, chemical oxygen demand (COD), biochemical oxygen demand (BOD) and BOD5/COD ratio were the parameters to evaluate the efficiency of the ozonation process. In addition, the toxic potential of the OTC degradation was investigated by the bioluminescence test using the LUMIStox 300 instrument and results were expressed as the percentage inhibition of the luminescence of the marine bacteria Vibrio fischeri. The results demonstrate that ozonation as a partial step of a combined treatment concept is a potential technique for biodegradability enhancement of effluents from pharmaceutical industries containing high concentration of oxytetracycline provided that the appropriate ozonation period is selected. At pH 11 and after 60min of ozonation of oxytetracycline aqueous solutions (100 and 200mgl(-1)) the BOD5/COD ratios were 0.69 and 0.52, respectively. It was also shown that COD removal rates increase with increasing pH as a consequence of enhanced ozone decomposition rates at elevated pH values. The results of bioluminescence data indicate that first by-products after partial ozonation (5-30min) of OTC were more toxic than the parent compound.     

Removal of selected endocrine disrupting chemicals and personal care products in surface waters and secondary wastewater by ozonation

This study investigated the removal of parabens, N,N-diethyl-m-toluamide (DEET), and phthalates by ozonation. The second-order rate constants for the reaction between selected compounds with ozone at pH 7 were of (2.2 +/-0.2) X 10(6) to (2.9 +/-0.3) X 10(6) M 1/s for parabens, (2.1+/- 0.3) to (3.9 +/-0.5) M-1/s for phthalates, and (5.2 +/-0.3) M-1/s for DEET. The rate constants for the reaction between selected compounds with hydroxyl radical ranged from (2.49 +/-0.06) x 10(9) to (8.5 +/-0.2) x 10(9) M-1/s. Ozonation of selected compounds in secondary wastewater and surface waters revealed that ozone dose of 1 and 3 mg/L yielded greater than 99% depletion of parabens and greater than 92% DEET and phthalates, respectively. In addition, parabens were found to transform almost exclusively through the reaction with ozone, while DEET and phthalates were transformed almost entirely by hydroxyl radicals (.OH).     

Estrogenic activity removal of 17beta-estradiol by ozonation and identification of by-products

This work investigated the degradation of a natural estrogen (17beta-estradiol) and the removal of estrogenic activity by the ozonation process in three different pHs (3, 7 and 11). A recombinant yeast assay (YES assay) was employed to determine estrogenic activity of the ozonized samples and of the by-products formed during the ozonation. Ozonation was very efficient for the removal of 17beta-estradiol in aqueous solutions. High removals (>99%) were achieved with low ozone dosages in the three different pHs. Several by-products were formed during the ozonation of 17beta-estradiol. However, only a few compounds could be identified and confirmed. Different by-products are formed at different pHs, which is probably due to different chemical pathways and different oxidants (O(3) and OH radical). The by-products formed at pH 11 were 10epsilon-17beta-dihydroxy-1, 4-estradieno-3-one (DEO) and 2-hydroxyestradiol, which were not formed in pH 3. Only testosterone could be observed in pH 3, whereas at pH 7 all three by-products were found. At pH 7 and 11 the applied ozone dosages were not enough to remove all the estrogenicity from samples, even though the 17beta-estradiol residual concentration for these two pHs was lower than at pH 3. Higher estrogenicity was detected at pH 11. An explanation to this fact may be that oxidation via OH radical forms more by-products with estrogenic activity. Probably, the formation of 2-hydroxyestradiol at pHs 7 and 11 is contributing to the residual estrogenicity of samples ozonized at these pHs. In this work, complete removal of estrogenic activity was only obtained at pH 3.     

Appropriate combination of physico-chemical methods (coagulation/flocculation and ozonation) for the efficient treatment of landfill leachates

An integrated technique consisted of ozonation and coagulation/flocculation processes was studied, aiming to provide an efficient method for the treatment of stabilized/biologically pre-treated leachates, in order to reduce the organic pollutants' content to concentration values lower than the corresponding limits, imposed by the legislation. Leachates were collected from a municipal landfill site; samples containing around 1000 mg l(-1) COD and BOD(5)/COD ratio about 0.17 were treated by using two different processes or combinations between them, i.e. ozonation, coagulation-flocculation, ozonation followed by coagulation/flocculation and coagulation/flocculation followed by ozonation. The application of single ozonation resulted to the efficient removal of color and organic loading, due to the respective oxidation, induced by ozonation; however, COD values lower than 200 mg l(-1) could be only achieved after prolonged reaction times and for high ozone production rates. The coagulation of leachate samples was studied by the addition of ferric chloride or poly-aluminum chloride agents at various dosages. Maximum COD removal rates (up to 72%) were achieved by the addition of 7 mM Fe, or of 11 mM Al respectively. However, final COD values higher than 200 mg l(-1) were obtained indicating the requirement of an additional treatment step. Pre-ozonation followed by coagulation/flocculation was not found to be an efficient treatment approach for this aim, but coagulation/flocculation followed by ozonation, was proved to be an efficient process for the reduction of COD to lower than 180 mg l(-1).     

臭氧氧化法处理焦化废水生化出水的反应动力学

对臭氧氧化去除焦化废水生化出水COD的反应动力学及其影响因素进行了实验研究,结果表明,在臭氧投加量为8．50mg／min,反应温度为20＇E和初始pH为10．61条件下,对COD的降解符合表观一级反应动力学模型,其相关系数R。=0．9991,表观反应速率常数k。。=1．01×10^-3s-1。该条件下,臭氧氧化对COD的降解主要来源于高活性羟基自由基的强氧化作用。在不同的臭氧投加量（4．25～12．75mg／min）、不同的反应温度（10～40℃）和不同的初始pH（3．76～12．53）下,COD的降解也同样遵循一级反应动力学规律。随着臭氧投加量的增大,COD降解的表观反应速率常数从（0．554×10^-3）s-1增加到（1．06×10＆-3）s-1;随着反应温度的升高,表观反应速率常数从（0．427×10^-3）s-1增加到（1．40×10-3）s-1,温度越高反应速率提高的幅度却越小;在初始pH3．76～10．61范围内,表观反应速率常数从（0．218×10^-3）s-1增加到（1．01×10^-3）s-1,在初始pH为12．53时表观反应速率常数下降到（0．857×10^-3）s-1。     

Formation of N-nitrosodimethylamine (NDMA) by ozonation of dyes and related compounds

Formation of N-nitrosodimethylamine (NDMA) by ozonation of commercially available dyes and related compounds was investigated. Ozonation was conducted using a semi-batch type reactor, and ozone concentration in gas phase and the ozone gas flow were 10 mg L(-1) and 1.0 L min(-1), respectively. NDMA was formed by 15 min of ozonation of seven out of eight selected target compounds (0.05 mM) at pH 7. All the target compounds with N,N-dimethylamino functions were NDMA precursors in ozonation. The lowest and highest NDMA concentrations after ozonation of the target compounds were 13 ng L(-1) for N,N-dimethylformamide (DMF) and 1600 ng L(-1) for N,N-dimethyl-p-phenylenediamine (DMPD), respectively. NDMA concentrations after 15 min of ozonation of 0.05 mM methylene blue (MB) and DMPD increased with an increase in pH in its range of 6-8. The effects of coexisting compounds on NDMA concentrations after 15 min of ozonation of 0.05 mM MB and DMPD were examined at pH 7. NDMA concentrations after ozonation of MB and DMPD increased by the presence of 0.05 mM (0.7 mg L(-1) as N) nitrite (NO(2)(-)); 5000 ng L(-1) for MB and 4000 ng L(-1) for DMPD. NDMA concentration after MB ozonation decreased by the presence of 5mM tertiary butyl alcohol (TBA), a hydroxyl radical (HO.) scavenger, but that after DMPD ozonation was increased by the presence of TBA. NDMA concentrations after ozonation of MB and DMPD were not affected by the presence of 0.16 mM (5.3 mg L(-1)) hydrogen peroxide (H(2)O(2)). When 0.05 mM MB and DMPD were added to the Yodo and Tone river water samples, NDMA concentrations after 15 min of their ozonation at pH 7 increased compared with those in the case of addition to ultrapure water samples.     

原位臭氧氧化污泥减量工艺的运行效能

采用ASBR/SBR原位臭氧污泥减量工艺,重点研究了原位臭氧氧化对SBR段污泥产率和出水水质的影响。两个相同的ASBR/SBR组合工艺同时运行,每隔3个周期向臭氧投加组SBR的曝气阶段原位间歇投加臭氧,臭氧投加量为0.027 g O3/g MLSS,连续运行40 d;对照组不投加臭氧作为对比。结果表明,原位臭氧氧化实现污泥减量约43.9%,臭氧投加组SBR段平均污泥产率系数为0.1447 g SS/g SCOD,而对照组为0.2580 g SS/g SCOD,投加组没有惰性污泥的累积,并且污泥沉淀性能得到改善。原位臭氧氧化对出水水质影响不大,投加组与对照组相比,臭氧投加3周期后的出水COD、NH4+-N、TN和TP平均值分别为47.8、0.76、14.1和6.4 mg/L,去除率分别下降了4%、2%、3%和7.7%,其中COD、NH4+-N和TN均能达到《城镇污水处理厂污染物排放标准》(GB18918-2002)一级A标准。     

Chemical oxidation of wastewater from molasses fermentation with ozone

Color removal from biologically pre-treated molasses wastewater by means of chemical oxidation with ozone has been investigated. Batch experiments have been performed in order to analyze the influence of ozone dosage and reaction time on color removal, molecular weight distribution and decolorization kinetics. Depending on the applied ozone dosage, color removal from 71% to 93% and COD reduction from 15% to 25% were reached after 30 min reaction time. TOC values remained constant throughout ozonation. Gel permeation chromatography corroborated that high molecular weight compounds, responsible for the brown color, were present in raw wastewater. UV spectral studies confirmed that these colored compounds were melanoidins. As a result of ozonation the concentration of chromophore groups decreased. Ozonation of synthetic melanoidin under the same experimental conditions provided similar color removal efficiencies. Pseudo-first order kinetics with respect to colored compounds were found.     

Treatment and detoxification of a sanitary landfill leachate

The leachate from an old sanitary landfill (Gramacho Metropolitan Landfill, Rio de Janeiro) was characterized and submitted to coagulation and flocculation treatment followed by ozonation and ammonia stripping. The performance of the treatment was assessed by monitoring the removal of organic matter (COD and TOC), ammonium nitrogen and metals. Detoxification was assessed by determining acute toxicity, using the following organisms: Vibrio fisheri, Daphnia similis, Artemia salina and Brachydanio rerio. Membrane fractionation was employed to infer the range of molecular masses of the pollutants found in the effluent, as well as the toxicity associated to these fractions. Of the techniques under investigation, coagulation and flocculation followed by ammonia stripping were the most effective for toxicity and ammonium nitrogen removal. Membrane fractionation was effective for COD removal; however, acute toxicity was almost the same in all the fractionated samples. Ozonation was moderately effective for COD removal, but significant toxicity removal was only attained when high ozone doses were used.     

Removal of pyrene and benzo(a)pyrene from contaminated water by sequential and simultaneous ozonation and biotreatment.

The removal of pyrene and benzo(a)pyrene from contaminated water by sequential and simultaneous ozonation-bioremediation techniques was investigated. During the sequential treatment, ozonation using 0.5 or 2.5 mg/L ozone was used as a pretreatment process, whereas, during the simultaneous treatment process, ozonation of hydrocarbon-contaminated water at a predetermined duration using 0.5 mg/L ozone was made in the presence of microbial biomass. Ozonation was not beneficial for the removal of pyrene. However, despite a decreased specific biodegradation rate, ozonation improved the overall elimination of benzo(a)pyrene during both treatment processes. The overall removal of benzo(a)pyrene increased from 23 to 91% after exposure of the water to 0.5 mg/L ozone for 30 minutes during the simultaneous treatment process and further to 100% following exposure to 2.5 mg/L ozone for 60 minutes during the sequential treatment mode, demonstrating the benefits of combined ozonation-biological treatment for the removal of polycyclic aromatic hydrocarbons.     

铁及铁铜氧化物对臭氧氧化酸性红B的催化效能

采用自蔓延溶胶凝胶法分别制备了铁氧化物和铁铜复合氧化物催化剂,以酸性红B为降解对象,对比了单独臭氧氧化、铁氧化物和铁铜复合氧化物催化臭氧氧化对酸性红B的降解效果,考察了磁力搅拌速度(500～1 640 r/min)、溶液pH(3～11)、臭氧投加速率(3.55～28.4 mg/min)对铁铜复合氧化物催化性能的影响。结果表明,与单独臭氧氧化比较,铁氧化物和铁铜复合氧化物均能加速酸性红B的降解,促进色度和COD的去除,结合催化剂的表征结果,推断催化剂表面羟基促进臭氧分解产生.OH是其氧化性能较好的主要原因,另外,催化剂的吸附能力对催化性能也有一定影响。随着磁力搅拌速度、溶液pH、臭氧投加速率的增大,铁铜复合氧化物催化臭氧氧化酸性红B的效果越好。     

Ozonation of hydrolyzed azo dye reactive yellow 84 (CI).

The combination of chemical and biological water treatment processes is a promising technique to reduce recalcitrant wastewater loads. The key to the efficiency of such a system is a better understanding of the mechanisms involved during the degradation processes. Ozonation has been applied to many fields in water and wastewater treatment. Especially for textile mill effluents ozonation can achieve high color removal, enhance biodegradability, destroy phenols and reduce the chemical oxygen demand (COD). However, little is known about the reaction intermediates and products formed during ozonation. This work deals with the degradation of hydrolyzed Reactive Yellow 84 (Color Index), a widely used azo dye in textile finishing processes with two monochlorotriazine anchor groups. Ozonation of the hydrolyzed dye in ultra pure water was performed in a laboratory scale cylindric batch reactor. Decolorization, determined by measuring the light absorbance at the maximum wavelength in the visible range (400 nm), was almost complete after 60 and 90 min with an ozone concentration of 18.5 and 9.1 mg/l, respectively. The TOC/TOC0 ratio after ozonation was about 30%, the COD was diminished to 50% of the initial value. The BOD5/COD ratio increased from 0.01 to about 0.8. Oxidation and cleavage of the azo group yield nitrate. Cleavage of the sulfonic acid groups of aromatic rings caused increases in the amount of sulfate. Formic acid and oxalic acid were identified as main oxidation products by high performance ion chromatography (HPIC). The concentrations of these major products were monitored at defined time intervals during ozonation.     

臭氧氧化6-APA制药厂生化处理出水的特性及动力学

通过现场实验研究了6-APA制药厂生化处理出水的臭氧氧化特性及其动力学规律。结果表明,当臭氧浓度为27．5mg／L,气水接触时间为80min时,COD、UV254、NH3-N和色度的去除率分别可达72．95％、73．28％、72％和96．25％,达到《发酵类制药废水工业水污染物排放标准》（GB21903—2008）排放控制要求。拟合结果表明,在0～10、10～30和30～90min时段内,臭氧氧化过程遵循拟一级反应,但反应速率逐渐降低。当气水接触时间为30min时,废水可生化性可由0．1提高至0．35,采用臭氧／生物处理的联合工艺也有望使出水达到相同的排放控制要求。     

臭氧预氧化-BAF工艺深度处理垃圾渗滤液

以广东省江门市垃圾填埋场垃圾渗滤液为研究对象,对经SBR生化处理和聚合硫酸铁混凝后的垃圾渗滤液,采用臭氧-BAF(曝气生物滤池)工艺进行深度处理。该工艺优点在于：臭氧高级氧化技术使大分子有机污染物降解成二氧化碳和水,或者小分子有机污染物,有利于后继BAF的生化处理,且臭氧处理过后废水的色度明显降低,是废水处理的有效方法之一。而后采用曝气生物滤池对垃圾渗滤液进行进一步处理,对COD进一步去除。结果表明,当臭氧的加入量为150 mg/L,BAF停留时间＞4 h,出水COD低于85 mg/L,稳定达到国家GB 16889-1997《生活垃圾填埋污染控制标准》一级排放标准,臭氧氧化法处理每吨垃圾渗滤液的费用为4.8元。     

臭氧/活性炭联合工艺深度处理焦化废水

采用臭氧/活性炭联合工艺对焦化废水A2/O出水进行深度处理。考察了溶液初始pH值、臭氧投加量、活性炭投加量及使用次数、反应时间对焦化废水处理效果的影响。实验结果表明,活性炭的使用可显著提高臭氧对焦化废水COD的去除率,在溶液初始pH值为10.25、臭氧投加量为7.5 mg/min、活性炭投加量50 g/L、反应时间为30 min条件下,COD去除率达到73.51%。同时,在活性炭重复使用10次时,COD去除率为70.85%,仅降低了2.66%。     

Treatment of pharmaceutical wastewater containing antibiotics by O3 and O3/H2O2 processes

Ozonation of three different synthetic pharmaceutical formulation wastewater containing two human antibiotics and a veterinary antibiotic has been studied to enhance the their biodegradability. The effects of pH and initial chemical oxygen demand (COD) value as well as addition of hydrogen peroxide on ozonation process were investigated. Total organic carbon (TOC), COD, biochemical oxygen demand (BOD), and aromatic content (UV254) were the parameters followed to evaluate the performance of ozonation process. Comparison of the biodegradability of selected wastewaters containing different antibiotics confirmed that the variation of biodegradability was associated with the target compound. While BOD5/COD ratio of veterinary antibiotic formulation wastewater was increased from 0.077 to 0.38 with an applied ozone dosage of 2.96 g/l, this ratio for human antibiotic I and human antibiotic II was increased from 0 to 0.1 and 0.27 respectively. Moreover the results of this investigation showed that the ozonation process is capable of achieving high levels of COD and aromaticity removals at about their natural pH values.     

臭氧氧化6-APA制药厂生化处理出水的特性及动力学简

通过现场实验研究了6-APA制药厂生化处理出水的臭氧氧化特性及其动力学规律。结果表明,当臭氧浓度为27.5 mg/L,气水接触时间为80 min时,COD、UV₂₅₄、NH₃-N和色度的去除率分别可达72.95%、73.28%、72%和96.25%,达到《发酵类制药废水工业水污染物排放标准》（GB 21903-2008）排放控制要求。拟合结果表明,在0~10、10~30和30~90 min时段内,臭氧氧化过程遵循拟一级反应,但反应速率逐渐降低。当气水接触时间为30 min时,废水可生化性可由0.1提高至0.35,采用臭氧/生物处理的联合工艺也有望使出水达到相同的排放控制要求。