畜禽养殖废水生物处理剩余污泥臭氧减量过程中的重金属释放简

采用臭氧氧化污泥减量法对畜禽养殖废水SBR中的剩余污泥进行处理。当臭氧反应时间控制在30 min时,污泥的溶解比例在30%左右（以 MLSS计）。上清液中一定量的SCOD溶出可为生物处理单元提供充足的碳源,同时在上清液中,TN、TP及水相重金属浓度增加有限,臭氧氧化后的污泥液回流污水处理系统后造成的N、P处理负荷较小,重金属对污泥微生物的活性抑制风险较低。若继续延长臭氧的反应时间,上清液SCOD、TN、TP以及重金属Cu、Pb的释放速率明显增加,同时上清液的C/N降低,臭氧化后的污泥液回流反而不利于生物单元的脱氮处理。综合考虑TN、TP及水相重金属浓度增加的危害性,臭氧反应时间应控制在30 min,臭氧实际投加量应为123.1 mg O₃/g SS。     

Influence of ozone pre-treatment on sludge anaerobic digestion: removal of pharmaceutical and personal care products

The effect of an oxidative pre-treatment with ozone on the removal of Pharmaceutical and Personal Care Products (PPCPs) during the anaerobic digestion of sewage sludge has been investigated. Besides, the digested sludge characteristics in terms of pathogens content, dewatering properties, heavy metals content and linear alkylbenzene sulfonates (LAS) were determined. During ozonation (20mg O(3)/g TSS), about 8% of volatile solids (VS) and 60% of the chemical oxygen demand (COD) were solubilized. However, no mineralization was observed. The elimination of VS and total COD during anaerobic digestion were not affected by ozone treatment with efficiencies ranging from 60% to 65%. All PPCPs considered were removed during anaerobic treatment of sludge, with efficiencies ranging from 20% to 99%. No significant influence of ozone pre-treatment was observed on PPCPs elimination except for carbamazepine. Pathogens, heavy metals and LAS contents after conventional and pre-ozonation treatment of sewage sludge were below the legal requirements. However, the dewatering properties of sludge were deteriorated when the ozone pre-treatment was applied.     

原位臭氧氧化对活性污泥系统硝化和反硝化作用的影响研究

将厌氧序批式间歇反应器(ASBR)和序批式间歇反应器(SBR)串联组成污泥减量新工艺,着重探讨了对SBR段进行原位臭氧投加时,臭氧氧化作用对系统硝化和反硝化能力的影响,并以不投加作为对照。结果表明,将臭氧原位投加到ASBR—SBR组合工艺的SBR段,臭氧投加量为0.027g(以每克MLSS计),每隔3个周期再次投加、连续运行40d,试验组SBR段臭氧投加当期出水COD去除率为86%,比对照组下降了9百分点,但臭氧氧化细胞内大量有机物进入混合液中,为反硝化作用提供了外加碳源,对污泥反硝化能力的提高起到了一定的促进作用;试验组部分硝化细菌由于臭氧的强氧化作用而失去活性,但是随着剩余污泥量的减少,系统的污泥龄延长,有利于硝化细菌的生长,使得系统的硝化能力基本未受影响;试验组臭氧投加当期SBR段出水NO2--N平均浓度比对照组的高18.9%,但经过3个周期的运行后,其SBR段出水NO2--N平均质量浓度降低至7.57mg/L,基本与对照组持平;试验组臭氧投加当期SBR段出水NO3--N的平均浓度高于对照组,但经过3个周期的运行后,试验组出水NO3--N平均浓度低于对照组;试验组臭氧投加当期SBR段出水TN和对照组的出水TN平均去除率分别为65%和75%,但试验组再经过3个周期的运行后,出水TN平均去除率可以达到72%。可见,原位投加臭氧并未对SBR段的硝化和反硝化能力产生明显的影响。     

畜禽养殖废水生物处理剩余污泥臭氧减量过程中的重金属释放

采用臭氧氧化污泥减量法对畜禽养殖废水SBR中的剩余污泥进行处理。当臭氧反应时间控制在30min时,污泥的溶解比例在30％左右（以MLSS计）。上清液中一定量的SCOD溶出可为生物处理单元提供充足的碳源,同时在上清液中,TN、TP及水相重金属浓度增加有限,臭氧氧化后的污泥液回流污水处理系统后造成的N、P处理负荷较小,重金属对污泥微生物的活性抑制风险较低。若继续延长臭氧的反应时间,上清液SCOD、TN、TP以及重金属cu、Pb的释放速率明显增加,同时上清液的C／N降低,臭氧化后的污泥液回流反而不利于生物单元的脱氮处理。综合考虑TN、TP及水相重金属浓度增加的危害性,臭氧反应时间应控制在30min,臭氧实际投加量应为123．1mg O3／gSS。     

Enhanced sludge solubilization by microbubble ozonation

A microbubble ozonation process for enhancing sludge solubilization was proposed and its performance was evaluated in comparison to a conventional ozone bubble contactor. Microbubbles are defined as bubbles with diameters less than several tens of micrometers. Previous studies have demonstrated that microbubbles could accelerate the formation of hydroxyl radicals and hence improve the ozonation of dyestuff wastewater. The results of this study showed that microbubble ozonation was effective in increasing ozone utilization and improving sludge solubilization. For a contact time of 80 min, an ozone utilization efficiency of more than 99% was obtained using the microbubble system, while it gradually decreased from 94% to 72% for the bubble contactor. The rate of microbial inactivation was obviously faster in the microbubble system. At an ozone dose of 0.02 g O₃ g⁻¹ TSS, about 80% of microorganisms were inactivated in the microbubble system, compared with about 50% inactivation for the bubble contactor. Compared to the bubble contactor, more than two times of COD and total nitrogen, and eight times of total phosphorus content were released from the sludge into the supernatant by using the microbubble system at the same ozone dosage. The application of microbubble technology in ozonation processes may provide an effective and low cost approach for sludge reduction.     

Changes in biomass activity and characteristics of activated sludge exposed to low ozone dose

In this paper, the response mechanism of activated sludge exposed to low-dose ozone at less than 20 mg O₃ g⁻¹ total suspended solids (TSS) was studied by analyzing the changes in sludge activity and the evolution of C, N, P and metals from sludge following ozonation. The intracellular ATP concentration was not affected at less than 5 mg O₃ g⁻¹ TSS and thereafter decreased rapidly to around 60% when the ozone dose increased to 20 mg O₃ g⁻¹ TSS. Similarly, the efficiency of sludge solubilization initially changed a little and then increased rapidly to around 30% at an ozone dose of 20 mg O₃ g⁻¹ TSS. However, the activities of superoxide dismutase and protease decreased immediately upon exposure to ozone. These findings indicate that ozone firstly destroys the floc, leading to the disruption of the compact aggregates, which does not affect cells viability but induces a decrease in enzyme activities. Ozone then attacks the bacterial cells of the sludge, causing a decrease in cells viability. During ozonation, the content of carbon, nitrogen and phosphorus in the sludge matrix decreased, while the content of these elements in the micro-solids and supernatant gradually increased. Most of the released metals from the sludge matrix were found in the micro-solids.     

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。     

Improved solubilization of activated sludge by ozonation in pressure cycles

The generation of a large volume of activated sludge (AS) from wastewater treatment has increasingly become a great burden on the environment. Anaerobic digestion is routinely practiced for excess waste sludge; however, the process retention time is long because of kinetic limitation in the hydrolysis step. We tested the feasibility of applying ozone in pressure cycles to enhance the disintegration and solubilization of AS with the goal to prepare them for digestion using reduced ozone dose and contact time. The AS was subjected to repetitive pressure cycles in a closed vessel in which an ozone gas mixture was compressed into the slurry to reach 1040 kPa in the headspace to be followed by rapid venting. For a returned AS with total COD (tCOD) of 8200 mg L(-1), a dose of 0.01 gO(3)g(-1) total suspended solids (TSS) delivered via 20 pressure cycles within 16 min resulted in a 37-fold increase of the sCOD/tCOD ratio (due to increased soluble COD, i.e. sCOD) and a 25% reduction of TSS, in comparison to a dose of 0.08 gO(3)g(-1) TSS via bubbling contact over 15 min that resulted in a 15-fold increase of the sCOD/tCOD ratio and a 12% reduction of TSS. Sludge solubilization was evidenced by increased dissolved contents of total phosphorous (from 10 to 64 mg L(-1)), total nitrogen (from 14 to 120 mg L(-1)), and protein (from <15 to 39 mg L(-1)) in the sludge suspension after treatment, indicating significant solubilization of AS.     

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).     

Ozone disintegration of excess biomass and application to nitrogen removal.

A pilot-scale facility integrated with an ozonation unit was built to investigate the feasibility of using ozone-disintegration byproducts of wasted biomass as a carbon source for denitrification. Ozonation of biomass resulted in mass reduction by mineralization as well as by ozone-disintegrated biosolids recycling. Approximately 50% of wasted solids were recovered as available organic matter (ozonolysate), which included nonsettleable microparticles and soluble fractions. Microparticles were observed in abundance at relatively low levels of ozone doses, while soluble fractions became dominant at higher levels of ozone doses in ozone-disintegrated organics. Batch denitrification experiments showed that the ozonolysate could be used as a carbon source with a maximum denitrification rate of 3.66 mg nitrogen (N)/g volatile suspended solids (VSS) x h. Ozonolysate was also proven to enhance total nitrogen removal efficiency in the pilot-scale treatment facility. An optimal chemical oxygen demand (COD)-to-nitrogen ratio for complete denitrification was estimated as 5.13 g COD/g N. The nitrogen-removal performance of the modified intermittently decanted extended aeration process dependent on an external carbon supply could be described as a function of solids retention time.     

Adverse effects of erythromycin on the structure and chemistry of activated sludge

This study examines the effects of erythromycin on activated sludge from two French urban wastewater treatment plants (WWTPs). Wastewater spiked with 10 mg/L erythromycin inhibited the specific evolution rate of chemical oxygen demand (COD) by 79% (standard deviation 34%) and the specific N-NH₄⁺ evolution rate by 41% (standard deviation 25%). A temporary increase in COD and tryptophan-like fluorescence, as well as a decrease in suspended solids, were observed in reactors with wastewater containing erythromycin. The destruction of activated sludge flocs was monitored by automated image analysis. The effect of erythromycin on nitrification was variable depending on the sludge origin. Erythromycin inhibited the specific nitrification rate in sludge from one WWTP, but increased the nitrification rate at the other facility.     

Ozonation of Procaine Penicillin G formulation effluent Part I: Process optimization and kinetics

Ozonation characteristics of synthetic Procaine Penicillin G (PPG) formulation effluent were investigated in a semi-batch ozone reactor at different pH (3, 7 and 12), ozone feed rates (600-2600 mg h-1) and COD values (200-600 mg l-1). Ozonation of aqueous PPG effluent resulted in 37 (82)% COD removal after 60 (120) min ozonation when the reaction pH was kept constant at pH=7.900 mg l-1 (corresponding to 50% of the total introduced) ozone was absorbed during a reaction period of 1 h. The effects of increasing the applied ozone dose and the initial COD on the COD abatement rates of PPG effluent were also studied. Results have indicated that increasing the ozone dose and decreasing the COD content both have positive effects on COD removal rates. The significant contribution of the free radical (.OH) reaction pathway to PPG ozonation could be traced using tert-butyl alcohol as the .OH probe compound at varying concentrations. The bimolecular reaction rate constants for the direct reaction of PPG with ozone were found as 152 and 2404 M-1 h-1 at pH=3 and 7, respectively, using the gas phase ozone partial pressures determined from of the outlet gas stream analysis. It could be demonstrated that ozone decomposition to free radicals being triggered by increasing the pH from 3 to 7 is essential for the rate enhancement of PPG effluent ozonation.     

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.     

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。     

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.     

Case study I: application of the divalent cation bridging theory to improve biofloc properties and industrial activated sludge system performance-direct addition of divalent cations.

The objectives of this study were to examine the application of the divalent cation bridging theory (DCBT) to improve settling, dewatering, and effluent quality in pilot-scale reactors and a full-scale system treating an industrial wastewater. This was accomplished by lowering the monovalent-to-divalent (M/D) cation ratio by direct divalent cation addition. Research has shown that the M/D ratio is a potential indicator for settling and dewatering problems at wastewater treatment plants, and M/D ratios above 2 have been associated with poor settling, dewatering, and effluent quality. The M/D ratio of the wastewater in this study ranged from 6 to 20. The cations studied were calcium and magnesium. Results showed that the addition of calcium improved floc properties compared to control reactors with no calcium addition. The reductions in sludge volume index, effluent chemical oxygen demand (COD), and effluent total suspended solids (TSS) were approximately 35, 34, and 55%, respectively, when the M/D ratio was decreased to approximately 2:1. In addition, the cake solids from a belt filter press simulator increased by 72% and the optimum polymer dose required for conditioning was reduced by 70% in the reactor fed the highest calcium concentration when compared to control reactors with no calcium addition. The addition of calcium also decreased the negative effect of high filamentous organism numbers. In general, the addition of magnesium (Mg2+) had similar effects on effluent quality and dewatering properties, although some differences were measured. A full-scale test using calcium addition was performed. Measurements of effluent quality and floc properties were performed before, during, and after the calcium (Ca2+) addition period. The average M/D ratio during these periods was 6.2, 4.6, and 14.0, respectively. The addition of Ca2+ decreased the effluent five-day biochemical oxygen demand, effluent TSS, and effluent COD. The increased Ca2+ concentration also improved dewatering measured by a decrease in specific resistance to filtration and capillary suction time. Overall, the addition of divalent cations to the pilot- and full-scale activated sludge systems improved floc properties and the data fit well with the DCBT.     

臭氧处理剩余污泥的减量化实验研究

采用质子交换聚合物膜电解法（PEM）产生臭氧,单独对剩余污泥进行氧化破解实验,结果表明,随着臭氧化反应时间的增加,污泥微生物细胞裂解,胞内物质进入到污泥溶液中,污泥固体物质减少,使得TS和VTS均显著下降,处理40 min后,其去除率分别达到57.33%和72.76%;SCOD前30 min呈线性增长,通入臭氧60 min后,由处理前的3 501.24mg/L上升到6 298.32 mg/L,增长率达79.88%;SV30及滤饼含水率均呈下降趋势,表明剩余污泥的沉淀性能及脱水性能得到明显改善。实验结果表明,直接利用臭氧对剩余污泥进行处理,可获得良好的减量化效果。     

臭氧对活性污泥特性影响研究

探讨了臭氧对于污水生物处理中活性污泥特性的影响。结果显示 ,随着臭氧化的进行 ,促进了活性污泥生物量的减少 ,并有一定量的生物污泥被无机化 ,并且污泥的活性和存活性降低了。其中臭氧投加量低于 0 .1gO3 /gSS时污泥活性即大幅下降 ,而后污泥浓度才随着臭氧量的增加而显著降低。     

Performance of anaerobic waste activated sludge digesters after microwave pretreatment.

Effects of microwave pretreatment on waste activated sludge (WAS) in mesophilic semicontinuous digesters with acclimatized inoculum at solids retention times (SRTs) of 5, 10, and 20 days are presented. Batch digesters determined optimum microwave temperature, intensity, WAS concentration, and percentage of WAS pretreated for highest WAS solubilization (soluble to total chemical oxygen demand ratio [SCOD:TCOD]) and biogas production. Pretreatment results indicated the potential to damage floc structure and release 4.2-, 4.5-, and 3.6-fold higher soluble proteins, sugars, and SCOD:TCODs compared with controls, with nucleic acid release. Pretreatment increased dewaterability and bioavailability of WAS with 20% higher biogas production compared with controls in batch digestion. In semicontinuous digesters, relative (to control) improvements in removals dramatically increased, as SRT was shortened from 20 to 10 to 5 days, with 23 and 26% higher volatile solids removals for WAS pretreated to 96 degrees C by microwave and conventional heating at a 5-day SRT.     

生物铁法去除维生素B1生产废水中COD的试验研究

生物铁法是一种新型的强化活性污泥法，处理高浓度、难生物降解维生素B1生产废水具有很大的优势。当进水COD浓度维持在8000mg／L时，COD的去除率可达94％以上，比普通活性污泥法高出9．7％。生物铁法污泥絮凝沉淀效果好，能保证系统有较高浓度的回流污泥，从而使曝气池的污泥浓度得到提高，COD的去除率也会相应地提高。