Nitrogen control in AO process with recirculation of solubilized excess sludge

In order to establish a sludgeless process with a nitrogen-controlled effluent, batch and continuous experiments in a lab scale anoxic-oxic (AO) process were carried out to investigate the possibility of ozonized sludge (OS) usage as a denitrification energy source. Through ozonation at an ozone dose of 1.2g O(3)/g MLVSS, 63.2% of treated MLVSS was solubilized, 12.7% of COD was lost (probably due to complete oxidation to CO(2)), and soluble COD/TN ratio of OS appeared to be only about 10.78 because ozonation released cellular proteins and other nitrogenous substances. In oxic conditions, incubation of OS supernatant with activated sludge generated nitrate without significant ammonia accumulation, which meant that rapid nitrification occurred following ammonia generation from heterotrophic degradation of nitrogen-bearing cellular substances. In anoxic conditions, externally supplied nitrate was removed at the expense of organic carbons in the OS supernatant. However, ammonia was accumulated as anoxic incubation proceeded probably because of heterotrophic degradation of nitrogenous materials as in oxic conditions. Thus it was appeared that solubilized excess sludge acted as a reducing power for denitrification but also as a nitrogen source. In addition, 24-41% of COD contained in OS supernatant were found to be consumed for denitrification. But the remaining COD was not assimilated further even in the presence of nitrate. It was concluded by a nitrogen balance analysis that the energy source contained in OS was not sufficient to completely reduce the nitrogen that was originated from OS itself to nitrogen gas.     

Purification of cork processing wastewaters by ozone,by activated sludge,and by their two sequential applications

Wastewaters generated in the cork processing industry were treated in continuous reactors by means of single treatments separately-a chemical ozonation and an activated sludge system-and then by both sequential processes-ozonation followed by aerobic degradation, and aerobic degradation followed by ozonation. The removals obtained in the ozonation alone were 12-54%, 65-81%, and 55-89% for the COD, total phenolics, and absorbance at 254 nm, respectively, while the consumed ozone yield ranged from 40% to 61%, and the biodegradability (BOD(5)/COD) varied from an initial 0.60 to final values between 0.68 and 0.93. The optimum hydraulic retention time and ozone partial pressure were 3 h and 3 kPa, respectively. The stoichiometric ratio was 0.56 g of organic substrate degraded per g of ozone consumed, while the rate constants obtained for the ozone disappearance and for the organic matter degradation were 4490 L g COD(-1) h(-1) and 1970 L g O(3)(-1)h(-1) respectively. The presence of hydrogen peroxide or UV radiation in addition to ozone increased the values of organic matter removal as well as the stoichiometric ratio and the rate constants. The aerobic treatment by the activated sludge system yielded COD removals between 13% and 37% for hydraulic retention times between 24 and 96 h, and the Contois model gave values of q(max)=0.14 g COD g VSS(-1)h(-1) and K(1)=22.6 g COD g VSS(-1) for the main kinetic parameters. The sequential processes increased the substrate removal efficiencies in comparison with the individual processes. These enhancements were greater in the aerobic degradation-ozonation sequence than in the ozonation-aerobic degradation sequence.     

Variations of respiratory activity and glutathione in activated sludges exposed to low ozone doses

Ozonation is one of the most effective treatments for reducing the production of activated sludges in wastewater treatment plants. However, because microorganisms are present in the form of microcolonies, some bacteria may be exposed to sub-lethal ozone doses that could lead to adaptation and resistance to further exposition to oxidative treatment. This represents a major question as it may limit the effect of the treatment, especially when low ozone doses are applied. The critical ozone dosage, defined as the lowest specific transferred ozone concentration leading to a decrease in the maximum oxygen uptake rate was estimated to range between 0.9 and 13.6mg O(3)g(-1) COD(sludges), according to the sludges tested. The lowest ozone dosage leading to the decrease of GSH and GSHt concentrations could be estimated to be lower than 10mg O(3)g(-1) COD(sludges) for GSH, and close to 10mg O(3)g(-1) COD(sludges) for GSHt. After sludge exposure to low ozone doses, no higher amounts of glutathione were synthesized, suggesting that no development of resistance to ozonation occurred after sludge treatment with low ozone doses.     

Removal and transformation of recalcitrant organic matter from stabilized saline landfill leachates by coagulation-ozonation coupling processes

The Bordo Poniente sanitary landfill in Mexico City currently receives 11,500 ton/day of solid wastes. The landfill has been in operation since 1985, in what was formerly Texcoco Lake, now a dried-up lakebed. The physico-chemical characteristics of the leachate generated by this particular landfill are altered by the incorporation of freatic saline water present in the area. This paper reports the results from a study evaluating coagulation and ozonation as alternative processes for removing and transforming recalcitrant organic matter from stabilized saline landfill leachate. Coagulation with ferric sulfate was found to remove up to 67% of COD and 96% of leachate color. The remaining 33% COD was removed with ozone. Recalcitrant organic matter removal by ozonation is limited by the reaction kinetic due mainly to ozone's low reactivity with the organic compounds present in the leachates (amines, amides, alcohols, aliphatic compounds, and carboxylic acids). However, ozone contributes greatly to changing the recalcitrant characteristics of organic matter. Leachate biodegradability was found to be significantly enhanced through ozonation: BOD(5) values reach 265%, and the BOD(5)/COD ratio increases from 0.003 to 0.015. Infrared analysis of ozonated leachates shows that the main by-products of recalcitrant organic matter ozonation are an increase in the hydroxyl and carboxylic groups, and the presence of aldehydes groups.     

Operational strategies for an activated sludge process in conjunction with ozone oxidation for zero excess sludge production during winter season

A pilot-scale activated sludge system coupled with sludge ozonation process was operated for 112 days of a winter season without excess sludge wasting. The concept of this process is that the excess sludge produced is first disintegrated by ozone oxidation and then recirculated to a bioreactor in order to mineralize the particulate and soluble organic compounds. The basis of operation was to determine either the optimal amount of sludge in kg SS ozonated each day (SO) or the optimal ozonation frequency under the variable influent chemical oxygen demand (COD) loading and temperature conditions, since the ozone supply consumes costly energy. The optimal SO was obtained using the theoretically estimated sludge production rate (SP) and experimentally obtained ozonation frequency (n). While the SP was mainly subject to the COD loadings, sludge concentration was affected by the temperature changes in winter season. The optimal n was observed between 2.5 and 2.7 at around 15 degrees C, but it was doubled at 10 degrees C. Mixed liquor suspended solids (MLSS) concentration was leveled off at around 5000 mg/L in bioreactor at 15 degrees C, but the volatile fraction of MLSS was fixed around 0.7 indicating that there was no significant inorganic accumulation. Suspended solids (SS) and soluble COD in effluents kept always a satisfactory level of 10 and 15 mg/L with sufficient biodegradation. It was recommended to apply a dynamic SO under variable influent COD loadings and temperature conditions to the activated sludge system without excess sludge production for saving energy as well as system stabilization.     

Study of catalyzed ozonation for advanced treatment of pulp and paper mill effluents

Ozonation and catalytic ozonation (TOCCATA process) were used as tertiary treatments of wastewaters from three different pulp and paper mills. Laboratory batch experiments were conducted to assess the efficiency of each oxidation system for removal of organic matter. The investigations measured ozone consumption rate, variations in chemical oxygen demand (COD), total organic carbon (TOC), suspended solids (SS) and molecular weight distribution with contact time. For conventional ozonation, ozone consumption rate was dependent on the nature of the effluent. Organic matter elimination occurred both by oxidation and precipitation. Precipitation played a major role on TOC removal varying with the effluent, and was responsible for production of high final SS concentrations. However, the effluent type did not affect the ozone consumption rate for TOCCATA-catalyzed reactions. Using TOCCATA, it was shown that organic matter was removed through steady conversion of organic carbon to carbon dioxide. Finally the two oxidation systems were compared with respect to their impact on molecular weight distribution. A total removal of the two initial fractions of compounds (high and low molecular weights) was observed with two effluents. With the third effluent, only the initial fraction of low molecular weight compounds was removed by the two oxidizing systems. The results showed that ozonation and TOCCATA-catalyzed ozonation could achieve removals of COD of 36-76%. Depending on the effluent type, the amount of ozone consumed per gram of COD removed was lower for conventional or for catalytic ozonation.     

The removal of estrogenic activity and control of brominated by-products during ozonation of secondary effluents

The purposes of this study were to investigate the behavior of brominated by-products, such as bromate ion and total organic bromide, formed during ozonation for the removal of estrogenic activity in sewage effluents and to propose operation parameters for the ozonation process. It is necessary to reduce the E(2) equivalent concentration of estrogenic activity in secondary effluent treated by 90% of the initial one. To do so, ozonation until dissolved ozone concentration increased to 0.1mg/L (which corresponds to approximately 1mg O(3)/mg DOC(0) [consumed ozone per initial DOC] of consumed ozone for the effluent in this study) is proposed as an operation parameter for ozonation without the formation of brominated by-products.     

Ozonation of naphthalene sulfonic acids in aqueous solutions. Part I: elimination of COD, TOC and increase of their biodegradability

Ozonation of 11 naphthalene sulfonic acids (NSA) in the aqueous solution was studied by bubbling at 31 degrees C at an ozone dose rate of 5.56 mg min(-1) l(-1). COD, TOC and BOD5 of these compounds were tested. It was found that COD and TOC can be removed effectively by ozonation as expected. More than 40% COD of compounds No. I (2-amino-1-NSA), No. 5 (1-hydroxy-7-amino-5-NSA), No. 6 (6-hydroxy-1-NSA), No. 8 (6-amino-1,4-naphthalene disulfonic acid) and No. 11 (I -hydroxy-6-amino-3-NSA) has been eliminated at an ozone dosage of 5.56 mg min(-1) l(-1) for 2 h. Although TOC removal was very different, a good biodegradability was reached for NSAs with an average ozone consumption of 3.0 mgl(-1) for a TOC0 concentration of 100 mg(-1). Ozonation and biotreatment should be good alternatives for these compounds, especially after 20% TOC reduction and TOC removal were more sensitive in predicting an increase in biodegradability during ozonation, than that of COD. NSAs are similar in their behavior with reference to ozone consumption. In order to obtain a good biodegradability of NSAs at a TOC0 concentration of 100 mgl(-1), an ozone consumption between 2.0 and 4.0 mg mg(-1) ACOD is needed for this setup and 3.0 mg O3 mg(-1) TOC0 requirement may be more practical in predicting the biological behavior of naphthalene compounds.     

ZnO/O3工艺降解水中微量有机物的研究

以实验室制备的粉末氧化锌(ZnO)为催化剂,考察了ZnO/O3工艺去除水中有机物的效能.采用总有机碳(TOC)指标反映水中有机污染物的含量.结果表明:臭氧投量为1 mg/L、ZnO投量为300 mg/L时,反应60 min后ZnO-O3工艺对TOC的去除率为46%,比单独臭氧化提高了1倍;反应温度明显影响该工艺对有机物的降解效果,在水温为5,10,20和25 ℃时,TOC的去除率分别为17.5%,31.5%,45.9%和51.3%.臭氧浓度和催化剂投量的增加,可以提高TOC的氧化降解效率.     

利用同步臭氧氧化实现SBR污泥减量的研究

将臭氧通入SBR反应器中进行同步臭氧氧化,考察了污泥的减量效果以及对出水水质的影响.结果表明:污泥产率随着臭氧投量的增加而减小,当臭氧投加量从零增加到O.04gO3/gSS时污泥产率从0.45 gSS/gSCOD减少到-0.04 gSS/gSCOD;同步臭氧氧化对SBR系统的出水水质没有显著影响,当臭氧投加量为0.03 gO3/gSS时系统对COD、NH4 -N、TP的去除率分别为92.5%、91.1%、80.5%.可见,同步臭氧氧化是实现污泥减量的有效方法.     

Ozone and photocatalytic processes to remove the antibiotic sulfamethoxazole from water

In this study, water containing the pharmaceutical compound sulfamethoxazole (SMT) was subjected to the various treatments of different oxidation processes involving ozonation, and photolysis and catalysis under different experimental conditions. Removal rates of SMT and total organic carbon (TOC), from experiments of simple UVA radiation, ozonation (O(3)), catalytic ozonation (O(3)/TiO(2)), ozone photolysis (O(3)/UVA), photocatalytic oxidation (O(2)/TiO(2)/UVA) and photocatalytic ozonation (O(3)/UVA/TiO(2)), have been compared. Photocatalytic ozonation leads to the highest SMT removal rate (pH 7 in buffered systems, complete removal is achieved in less than 5min) and total organic carbon (in unbuffered systems, with initial pH=4, 93% TOC removal is reached). Also, lowest ozone consumption per TOC removed and toxicity was achieved with the O(3)/UVA/TiO(2) process. Direct ozone and free radical reactions were found to be the principal mechanisms for SMT and TOC removal, respectively. In photocatalytic ozonation, with buffered (pH 7) aqueous solutions phosphates (buffering salts) and accumulation of bicarbonate scavengers inhibit the reactions completely on the TiO(2) surface. As a consequence, TOC removal diminishes. In all cases, hydrogen peroxide plays a key role in TOC mineralization. According to the results obtained in this work the use of photocatalytic ozonation is recommended to achieve a high mineralization degree of water containing SMT type compounds.     

臭氧投量对活性污泥特性参数的影响

通过试验分析和探讨了臭氧投量对活性污泥特性参数的影响.结果表明,随着臭氧投量的增加,SS和VSS呈明显降低的趋势,而活性污泥上清液中的SCOD、蛋白质、总氮及硝酸盐氮则增加;氨氮浓度总体上随臭氧投量的增加而增加,但在投量为95～137 h mgO3/gSS时有所下降,随后又明显增加;当臭氧投量<137 mgO3/gSS时,亚硝酸盐氮呈增加趋势,随后开始明显降低;当臭氧投量<211 mgO3/SSS时,TOC和多糖随臭氧投量的增加而增加,随后开始下降.     

pH sequential ozonation of domestic and wine-distillery wastewaters

Domestic and wine-distillery wastewaters were treated by semi-batch and continuous pH sequential ozonations. The process involves a succession of acidic and alkaline wastewater pH conditions. The alkaline periods allow oxidation of organic matter by hydroxyl radical and produce carbonates that eventually would inhibit the oxidation. On the other hand, the acidic periods favour the development of direct ozone reactions and strip off carbonates as carbon dioxide from the wastewater. Experimental results of pH sequential ozonation showed degradation and removal rates of wastewater pollutants higher than those achieved at constant either acidic or basic pH. The most significant improvement of ozone efficiency and pollutants removal were obtained by controlling the number of cycles, pH and time of acidic and alkaline phases. Also, ozonated wastewaters showed high biodegradability as deduced from their BOD/COD ratios. The feasibility of treating domestic and wine-distillery wastewater by an integrated activated sludge (ASP)-pH sequential ozonation system was evaluated. Integrated ASP-ozonation at constant pH processes were also carried out for comparative purposes. In these combined experiments, pH sequential ozonation showed advantages compared to ozonation at constant pH in reducing global parameters such as COD, TOC and TKN, but ozonation at constant pH led to higher removal of polyphenols and UV254 absorbing compounds.     

Mineralization of some natural refractory organic compounds by biodegradation and ozonation

The objective of this study was to explore the extent of mineralization, reduction in color and reduction of COD of gallic acid, tannin and lignin by ozonation and a combination of aerobic biodegradation and ozonation. Ozonation of pure aliquots (phase I experiments) resulted in the decline in TOC, COD, COD/TOC ratio, UV absorbance at 280 nm and color of the three model compounds investigated, with COD removals of greater than 80% and high removals (>90%) of UV absorbance at 280 nm and color observed in all cases at an ozone dose of 6 mg ozone/mg initial TOC or higher. Aerobic biodegradation of pure gallic acid, tannin and lignin aliquots resulted in COD decline of approximately 36-38%. Subsequent ozonation (phase II experiments) resulted in further decline in TOC, COD, COD/TOC ratio, and increase in UV absorbance at 280 nm and color removals. COD and TOC removals comparable to phase I experiments were obtained with 30-40% lower ozone absorption in phase II experiments. The biodegradation step was quite effective in removing specific UV absorbance at 280 nm, with up to 75% removal observed. Subsequent ozonation increased overall specific UV absorbance at 280 nm to greater than 90%.     

Integrated ozone and biotreatment of pulp mill effluent and changes in biodegradability and molecular weight distribution of organic compounds

The overall effectiveness of integrating ozonation with biological treatment on the biodegradability enhancement and recalcitrant organic matter (ROM) removal from pulp mill alkaline bleach plant effluent was investigated. Ozonation was performed in a semi-batch bubble column reactor at pH of 11 and 4.5. Batch biological treatment was conducted in shake flasks. Samples obtained during the treatments were monitored for BOD₅, COD, TOC, and molecular weight distribution. At an ozone dosage of 0.7-0.8 mg O₃/mL wastewater, integrated treatment showed about 30% higher TOC mineralization compared to individual ozonation or biotreatment. Ozone treatment enhanced the biodegradability of the effluent (monitored as 21% COD reduction and 13% BOD₅ enhancement), allowing for a higher removal of pollutants. The conversion of high molecular weight (HMW) to low molecular weight (LMW) compounds was an important factor in the overall biodegradability enhancement of the alkaline effluent. The overall biodegradability of the LMW compounds did not change over the course of ozonation, but it increased from 5% to 50% (measured as COD removal) for the HMW portion. Ozonation at pH of 11 was more effective than that at pH of 4.5 in terms of generating more biodegradable compounds.     

Removal of pharmaceuticals and kinetics of mineralization by O(3)/H(2)O(2) in a biotreated municipal wastewater

The ozonation of an effluent from the secondary clarifier of two Municipal Wastewater Treatment Plants was performed by using alkaline ozone and a combination of ozone and hydrogen peroxide. Alkaline ozonation achieved only a moderate degree of mineralization, essentially concentrated during the first few minutes; but the addition of hydrogen peroxide eventually led to a complete mineralization. The evolution of total organic carbon (TOC) as a measure of the extent of mineralization and the concentration of dissolved ozone were analyzed and linked in a kinetic model whose parameter represented the product of the exposure to hydroxyl radicals and the kinetic constant of indirect ozonation. This rate parameter yielded the highest values during the first part of O(3)/H(2)O(2) runs. The kinetic constant for the decomposition of ozone at the end of the run was also measured and computed for the non-oxidizable water matrix and yielded essentially the same values regardless of whether or not hydrogen peroxide was used. A group of 33 organic compounds, mainly pharmaceuticals and some relevant metabolites present in the wastewater effluents, were evaluated before and after the ozonation process using a liquid chromatography-hybrid triple-quadrupole linear ion trap system (LC-QqLIT-MS). The results demonstrate that the ozonation degrades these compounds with efficiencies of over 99% in most cases, even under low mineralization conditions in alkaline ozonation.     

Evaluation of the prediction of trace organic compound removal during ozonation of secondary effluents using tracer substances and second order rate kinetics

The application of the R_CT-concept for predicting the removal of trace organic compounds (TrOCs) in organic rich WWTP effluents is often problematic due to the fast ozone depletion with instantaneous ozone demand in the range of typically applied ozone dosages. In this study, the determination of OH-radical and ozone exposure from second order rate kinetics with two internal tracer substances was evaluated as alternative approach for these waters. Results from batch and semi-batch experiments showed a linear correlation of OH-radical exposure with ozone consumption, characterized by its slope indicating the formation efficiency of OH-radicals and a lag ozone consumption without significant formation of OH-radicals. Evaluation of data from the project PILOTOX on ozonation of secondary effluent confirmed reasonable prediction of ozone resistant compound removal from relative residual concentration of an internal tracer substance. In contrast, predicting the reduction of TrOCs by direct reactions with ozone from internal tracers was not feasible. Similar removal efficiencies for fast reacting compounds with different rate constants from k_O3 = 10⁴ M⁻¹ s⁻¹ to k_O3 = 10⁶ M⁻¹ s⁻¹ were observed indicating a limitation of the reaction by mass transfer. This effect was observed at low ozone dosages in semi-batch and pilot experiments as well as in batch experiments, where mass transfer from gas to liquid phase is not limiting. It is assumed that consumption of low ozone dosages is faster than sample homogenization in the batch reactors used. Thus, prediction of compound removal by direct reaction with ozone always needs to consider reactor design and geometry.     

亚硝酸盐氮对臭氧氧化有机物的影响研究

在臭氧氧化处理微污染原水的工艺中，臭氧对有机物的去除效果与水中还原性无机物的含量有关。通过试验考察了水中NO2^--N对臭氧氧化有机物的影响。结果表明，水中较高浓度的NO2^--N可消耗臭氧投加量的40％左右，并降低了臭氧对THMs前体物的去除率，也影响其提高水中可生物降解有机物浓度的能力；碱度的增加可增强NO2^--N对臭氧的竞争利用，降低臭氧对TOC和UV254的去除率。     

CASS工艺处理高校生活污水的试验研究

为了优化CASS工艺的运行参数,通过正交试验重点研究了污泥负荷、污泥沉降比(SV)、DO浓度、曝气时间等对COD、氨氮和TP去除效果的影响。结果表明,CASS工艺对有机物的去除效果较好,且抗冲击负荷能力较强;污泥负荷和SV值对COD、氨氮和TP去除效果的影响较大,而曝气时间和DO浓度的影响相对较小;试验条件下,CASS工艺的最佳运行参数如下:污泥负荷为0.50 kgCOD/(kgMLSS·d)、SV值为32%、曝气时间为2.5～3.0 h、DO为2.0～2.5 mg/L。     

Elimination of resin acids by advanced oxidation processes and their impact on subsequent biodegradation

Wood pulping and paper production generate a considerable amount of wastewater, containing many pollutants among them resin and fatty acids. Resin acids contribute substantially to effluent toxicity and were identified to be detrimental to microorganisms of activated sludge and in particular to bacteria in anaerobic wastewater treatment system and other forms of aquatic life. The objective of the present study was to check the applicability of the ozone and advanced oxidation processes (AOPs) to eliminate resin acids from aqueous solutions and to determine the ozone dose required. Furthermore, an investigation of the influence of the oxidation methods on subsequent biological destruction of the byproducts was performed. Aqueous solution of the resin acids: abietic, dehydroabietic and isopimaric acids with different initial composition were subjected to ozonation or AOP processes at different ozone doses. After ozonation or advanced oxidation pretreatment the model solutions were biodegraded in aerated vessels containing activated sludge. During ozonation of the resin acids aqueous solutions the resin acids were almost eliminated, however the reduction of chemical oxygen demand (COD) was rather low. The ozone dose required to obtain reduction of resin acids >90% was in the range of 0.1-0.7mgO(3)/mgCOD, depending on the composition and concentration of model solutions. The toxicity of ozonated resin acids solutions decreased with increasing applied ozone dose up to about 0.3-0.5mgO(3)/mgCOD, thereafter increased. Ozonation and other AOP processes did not increase the rate of biodegradation of resin acids model solutions in aerated activated sludge systems compared to not pretreated solutions.