Treatability of cefazolin antibiotic formulation effluent with O3 and O3/H2O2 processes.

The effect of applying ozonation and perozonation to antibiotic cefazolin-Na formulation effluents were investigated in this study. Twenty minutes of ozonation at a rate of 1,500 mg/L-h was observed to remove COD by 38%, whereas a COD removal efficiency of 40% was achieved via H2O2 enhanced ozonation (same conditions + 31.25 mM H2O2). Both of the pretreatment alternatives were monitored to elevate the BOD5/COD ratio from 0.01 to 0.08. The initially inert COD was reduced by 38% using ozonation and by 60% employing H2O2 enhanced ozonation. In terms of the lowest achievable effluent COD levels after bio-treatment, ozonation was observed to yield a residual COD of 205 mgL(-1), while a residual COD of 135 mgL(-1) was involved for perozonation. According to the results of acute toxicity on Phaedactylum tricornutum, ozonated and perozonated samples exhibited more toxicity than the untreated effluent after 4 days. The activated sludge inhibition test demonstrated that both of the pretreatment alternatives efficiently eliminated the inhibition of investigated formulation effluent.     

Effect of ozone, chlorine and hydrogen peroxide on the elimination of colour in treated textile wastewater by MBR.

In treating textile wastewater, the application of membrane bioreactor (MBR) technology showed high efficiency in COD and BOD5 removal. However, insufficient colour removal was achieved for possible reuse. The aim of the work presented in this paper was to test the performance of chemical advanced oxidation on the elimination of the colour downstream of an MBR. To improve the quality of the membrane bioreactor effluent three different oxidation treatments were tested at lab-scale: ozonation, chlorination and hydrogen peroxide oxidation. Colour, COD and BOD5 were controlled in order to assess the effectiveness of each process. For chlorination, even with 250 mg/L (active chlorine) only 80% colour removal (SACin = 14; SACout = 2.8) was achieved which is considered unsatisfactory. For hydrogen peroxide, the colour removal was even poorer; it was just 10% at a concentration of 250 mg/L. In contrast, good results were obtained by ozonation. By using only 38 mg/L within 20 minutes, it was possible to achieve the reuse recommendation with a satisfactory colour removal of 93% (SACin = 14; SACout = 0.98). The results showed that ozonation was the most promising method.     

Advanced oxidation of commercial textile biocides in aqueous solution: effects on acute toxicity and biomass inhibition.

In the present study, the decomposition of two biocides used in the textile finishing process with Advanced Oxidation Processes (AOPs) has been studied. Different AOPs, i.e O3/OH-, TiO2/UV-A and Fe2+/H2O2 have been used representing mutually combined components of the chemically and photochemically driven advanced oxidation systems. The course of reaction was examined by changes in chemical oxygen demand (COD), total organic carbon (TOC) and acute toxicity towards the water flea Daphnia magna (assessed in terms of the effective dilution ratio LD50). Particular attention has been paid to determine the inhibitory effect of raw and ozonated biocides on biological activated sludge consortium at concentrations typically encountered in textile finishing effluents. Significant oxidation and mineralization of both biocides could be achieved employing ozonation at pH = 11.5 and heterogeneous photocatalysis (TiO2/UV-A) at pH = 5.0, whereas Fenton's reagent appeared to be less effective in COD and acute toxicity abatement.     

Combined chemical biological treatment of bleached eucalypt kraft pulp mill effluent.

Effectiveness of ozonation before and after biological treatment for removal of recalcitrant organic matter in bleached kraft pulp effluents was compared. Two industrial ECF bleached eucalypt kraft pulp effluents (E1 and E2) were pretreated with 100 mg O3/L. Raw and pretreated effluents were treated biologically in bench-scale sequencing batch reactors, under constant conditions. Following biological treatment, effluents were post-treated with 100 and 200 mg O3/L. Effluent pretreatment increased effluent biodegradability by 10% in E1 and 24% in E2. Combined O3-biological treated led to small but significant increases in COD, BOD and lignin removal over biological treatment alone, but pretreatment had no significant effect on effluent colour and carbohydrate removal. Ozone pretreatment did not affect biological activity during treatment of effluent E1 but resulted in a 38% lower specific oxygen uptake rate in effluent E2. At an equivalent dose of 100 mg/L, pre-ozonation produced better quality effluent than post-ozonation, especially with regard to COD and colour. Likewise, when an equivalent dose of 200 mg/L was applied, splitting the dose equally between pre- and post-treatments was more efficient than applying the entire dose in the post-treatment. The potential for combined chemical-biological treatment to improve effluent quality has been confirmed in this study.     

Effects of sludge retention time and biosurfactant on the treatment of polyaromatic hydrocarbon (PAH) in a petrochemical industry wastewater

A laboratory-scale aerobic activated sludge reactor (AASR) system was employed to investigate the effects of sludge retention time (SRT) on the removal of three polyaromatic hydrocarbons (PAHs) with low benzene rings [(acenaphthene (ACT), fluorene (FLN) and phenanthrene (PHE)] and six PAHs with high benzene rings [(benzo[b]fluoranthene (BbF), benzo[k]fluoranthene (BkF), benzo[a]pyrene (BaP), indeno[1,2,3-cd]pyrene, dibenz[a,h]anthracene (DahA), benzo[g,h,i]perylene (BghiP)] in the presence of rhamnolipid (RD), emulsan (EM) and surfactine (SR) biosurfactants. This study showed that biosurfactants enhance the PAH biodegradation by increasing the biomass growth. RD exhibits a better performance than the other biosurfactants in the removal of the chemical oxygen demand (COD) and PAHs. At a RD concentration of 15 mg/L aerobic treatment for 25 days, SRT was enough to remove over 95% of total PAHs, and COD(dis). Under the same conditions 75% of COD originating from the inert organics (COD(inert)) and 96% of COD originating from the inert soluble microbial products (COD(imp)) were removed. At 25 days SRT and 15 mg/L RD concentration, about 88% of PAHs were biodegraded by the AASR system, 4% were accumulated in the system, 3% were released in the effluent, and 5% remained in the waste sludge.     

Effects and mechanism of ozonation for degradation of sodium acetate in aqueous solution

The degradation efficiencies and mechanism of ozonation for the degradation of sodium acetate in aqueous solution were investigated under atmospheric pressure at room temperature (293 K). The effects of the initial pH value, reaction time, and concentrations of HCO3-, CO32-, CaCl2, and Ca(OH)2 on the removal rate of chemical oxygen demand (COD) were studied. The results indicated that ozonation obviously improved the degradation rate of sodium acetate when the pH value of the solution was not less than 8.5. A suitable long reaction time may be helpful in increasing the COD removal rate, and a removal rate of 36.36% can be obtained after a 30-minute treatment. The COD removal rate increased firstly and decreased subsequently with the increase of the HCO3- concentration (from 0 to 200 mg/L), and under the same experimental condition it reached the optimum 34.66% at the HCO3- concentration of 100 mg/L. The COD removal rate was 5.26% lower when the concentration of was 200 mg/L than when there was no HCO3-. The COD removal rate decreased by 15.68% when the CO32- concentration increased from 0 to CO32- 200 mg/L. has a more obvious scavenging effect in inhibiting the formation of hydroxyl radicals than HCO3-. CaCl2 and Ca(OH)2 could increase the degradation efficiency of sodium acetate greatly, and the COD removal rates reached 65.73% and 83.46%, respectively, after a 30-minute treatment, 29.37% and 47.10% higher, respectively, than with single ozone oxidation. It was proved that the degradation of sodium acetate in the ozonation process followed the mechanism of oxidization with hydroxyl free radicals (·OH).     

Effect of photochemical pre-treatment on COD fractionation of a non-ionic textile surfactant.

The work presented in this paper is focused on the effect of photochemical (H2O2/UV-C) pretreatment on COD fractionation and degradation kinetics of a non-ionic textile surfactant. In the first part of the study, the COD of non-ionic surfactant was adjusted to 1000 mg/L in order to simulate real effluent originating from the textile preparation stage featuring desizing, scouring, washing and rinsing operations. The surfactant was subjected to H2O2/UV-C pretreatment for up to 120 min at a dose of 30 mM (980 mg/L) H2O2. The biodegradability studies for untreated and photochemically treated samples were evaluated on the basis of modeling of oxygen uptake rate (OUR) profiles. Modelling of OUR profiles conducted for untreated sample showed that single complex substrate was subjected to enzymatic breakdown and disintegrated into one readily and two types of slowly biodegradable substrates. After modelling the biodegradation of photochemically pretreated sample, the readily biodegradable COD fraction was reduced, on the other hand, more slowly biodegradable organics were generated. A higher disintegration rate was obtained for chemically pretreated samples. However, other kinetic constants of growth and hydrolysis processes were not affected considerably.     

Three stages MBR (methanogenic, aerobic biofilm and membrane filtration) for the treatment of low-strength wastewaters

The use of a new three stages MBR process with a first methanogenic UASB stage, a second stage with aerobic biofilm growing on small carrier elements maintained in suspension and third stage with membrane filtration module is presented. The objective of the first methanogenic chamber is to diminish COD of the raw wastewater, producing a biogas rich in methane, and decrease the sludge production. In the second stage, the remaining soluble biodegradable COD is oxidized by heterotrophs. In the third stage, the membrane modules could be operated at higher fluxes than those reported for AnMBR systems, and similar to those obtained in aerobic MBRs. In this sense, the concept of these three stages MBR is to join the advantages of the methanogenic and aerobic membrane bioreactor processes, by reducing energy requirements for aeration, producing biogas with high methane percentage and a permeate with very low COD content. A synthetic wastewater was fed to the three stages MBR. COD in the influent was between 200 and 1,200 mg/L, ammonium ranged from 10 to 35 mg/L and phosphorous concentration was 8 mg/L. OLR in-between 1 and 3 kg COD/(m3 d) and a HRT of 13-21 h were applied. Temperature was between 17.5 and 23.2 degrees C. During the whole operating period the COD removal efficiencies were in the range of 90 and 96% of which in between 40 and 80% was removed in the first methanogenic chamber. Biogas production with methane content between 75 and 80% was observed. With regard to membrane operation, average permeabilities around 150 L/(m2 h bar) were achieved, operating with fluxes of 11-15 L/(m2 h).     

臭氧氧化工艺溴酸盐控制中试研究

通过1m3/h的中试装置研究了臭氧氧化工艺处理引黄水库水时溴酸盐控制技术。结果表明,在臭氧投加量为1.5mg/L时,臭氧氧化后溴酸盐产生量为0.006mg/L,活性炭过滤出水溴酸盐为0.002mg/L;在相同臭氧投加量条件下,降低原水pH、投加高锰酸钾和过氧化氢后溴酸盐生成量分别减少了50%、33%和100%,活性炭后出水中均未检出溴酸盐,同时提高了有机物去除率。     

Recalcitrant COD degradation by an integrated system of ozonation and membrane bioreactor.

In order to treat wastewater to a low residual COD-concentration such as 125 mg/L, classical biological treatment is not sufficient for many types of industry. This research focused on the integrated treatment of the wastewater of the paper industry, with a membrane bioreactor (MBR) and an oxidation step. The optimal configuration was examined. Screening tests with different types of oxidation showed that ozonation after biological treatment could reduce the COD with 40% with an ozone dose of 0.4-0.8g O3/g COD. BOD/COD ratio could be increased up to 0.19. Neither combination of ozone with UV and/or hydrogen peroxide nor the process H2O2/UV or (photo-)Fenton reagents gave any improvement in COD reduction or BOD increase, unless the doses were very high. Based on these results, an integrated system MBR-ozonation was designed, with recirculation of MBR effluent over ozonation. This test showed that reduction of COD up to 125 mg/L immediately behind the MBR required a lot of ozone. A technically feasible solution was to discharge the water after an extra ozonation step, which resulted in a high total ozone dosage. The alternative, the consecutive treatment activated sludge-ozonation-activated sludge, did not give a better COD-removal with the same ozone dose as the integrated concept. The economic evaluation proves that the integrated chemical and biological treatment is expensive for the paper industry if a low discharge limit of COD has to be complied with.     

Effect of Fenton's treatment on the biodegradability of chromium-complex azo dyes.

Pretreatment of an acid dyebath effluent bearing a new generation chromium complex azo dyestuff (C0 = 350 mg/L) with Fenton's reagent was investigated. Preliminary optimisation (baseline) experiments were conducted to determine the Fe2+, H2O2 concentrations and pH required to the highest possible COD and colour removals. Kinetic studies were carried out at varying temperatures (20 degrees C < T < 70 degrees C) to establish a relationship between COD abatement and H2O2 consumption. The activation energy found for catalytic H2O2 decomposition (Ea = 9.8 kJ/mol) appeared to be significantly less than that of fermentative (Ea = 23 kJ/mol) and of thermal (Ea = 76 kJ/mol) H2O2 decomposition, implying that H2O2 decomposition during the Fenton's reaction occurs more spontaneously. The experimental studies indicated that approximately 30% COD and complete colour removal could be achieved under optimised Fenton pretreatment conditions (Fe2+ = 2 mM; H2O2 = 30 mM; pH = 3; at T = 60 degrees C). Long-term activated sludge experiments revealed that although the raw and pretreated acid dyebath effluent contained practically the same amount of "readily biodegradable" COD (inert COD fraction < or = 10%), biodegradation of the chemically pretreated acid dye effluent proceeded appreciably faster than that of the untreated acid dyebath effluent.     

Biological treatability of raw and ozonated synthetic penicillin formulation effluent.

Chemical pre-treatment of synthetic Procaine Penicillin G (PPG) effluent with ozone (applied dose = 1440 mg/h; treatment duration = 60 min) at pH = 7 was investigated. Successive biological treatability studies were performed with raw, ozonated penicillin formulation effluent and synthetic readily biodegradable substrate as simulated domestic wastewater. The PPG effluent additions were adjusted to constitute approximately 30% of the total COD in the reactor. Ozonation of PPG effluent resulted in practically complete removal of the parent pollutant accompanied by 40% COD abatement. Speaking for the raw PPG effluent, prolonged acclimation periods were necessary to obtain significant COD removal efficiencies. Batch activated sludge treatment experiments and respirometric studies have demonstrated that the selection of true retention time is extremely crucial for having high amount of slowly hydrolysable substrate or complex wastewater, like pharmaceutical effluent. The effect of ozonation time on biological treatability performance of PPG has been evaluated in the study. Pre-ozonation of PPG effluent did not improve its ultimate biodegradability.     

铁炭微电解-Fenton试剂氧化-二级A/O工艺处理化工废水工程实例

采用铁炭微电解结合Fenton试剂的化学氧化做预处理,二级A/O结合PACT工艺做后处理,混凝沉淀做辅助处理工艺处理含硝基苯的化工废水。介绍了工艺流程、主要参数和运行效果,同时讨论了该工艺的影响因素。工程监测结果表明:设计进水水量为600im~3/d,COD为5000mg/L时,预处理出水COD降至约1500mg/L,BOD/COD从0.1上升到0.3以上,后处理出水COD约为150mg/L,辅助处理出水COD小于100mg/L,COD总去除率可达97％。该工艺根据废水呈酸性的特点并合理利用废铁刨花,具有以废治废的特点,处理效果好,成本低,操作维护方便。     

Effect of chemical and biological treatment on COD fingerprints of textile wastewaters.

Particle size distribution (PSD) via sequential filtration/ultrafiltration was used as the tool for COD fractionation and colour profiling of textile wastewaters before and after treatment. Profiles prior to treatment suggested PSD-based COD fingerprints characteristic for the influents. Treatment efficiencies were determined via comparing the profiles of the effluents from chemical- and biological-treatment to those of the corresponding influents. COD fingerprints of the wastewaters from the textile plants, applying different treatment alternatives, were different especially at the upper size range; yet profiles after treatment were similar, with the soluble fraction (< 2 nm) being almost the only apparent one. Half of the overall COD-removal via chemical treatment was at the particulate- and upper colloidal-ranges, revealing that this alternative was effective at higher ranges, but not at the soluble fraction. In contrast, biological treatment was effective at both ends of size distribution, with total removal at the particulate range and 50% elimination at the soluble portion. Overall colour content and PSD-based colour profiles of the influents were also different. Chemical treatment was successful in removing colour originating from the entire colloidal range, but was not efficient at the soluble fraction. Conversely, colour removal efficiency of biological treatment was moderate throughout the entire size spectrum.     

常州市湖塘纺织工业园降雨径流污染负荷分析

我国当前以实现分流制为规划指导原则,分流制下工业园区雨水径流污染对水环境存在较大潜在影响。在此背景下采用SWMM软件模拟降雨和实地调研相结合的方法,分析湖塘园区降雨径流的污染负荷。结果表明:0.25年一遇的降雨径流质量浓度峰值ρ(TN)=6.01 mg/L,ρ(TP)=0.02 mg/L,ρ(COD)=125.21 mg/L,该降雨重现期下的TN和COD浓度均远劣于GB 3838—2002《地表水环境质量标准》的Ⅴ类水标准;随着降雨重现期增大,径流污染物浓度峰值会进一步提高。排入受纳水体采菱港的污染物总量比例:径流中TN占园区总TN(径流+点源)排放量的25.9%,径流中TP占4.4%,COD占28.0%,COD、TN径流污染量占整个园区污染总量的比重较大。结合湖塘园区排水系统的实地调研,建议加强园区初期雨水截留、推广园区中水回用和推进园区与企业排口设置规范化,以有效降低园区雨水径流对周边水环境的影响。     

The effect of oxidants on 2-MIB concentration with the presence of cyanobacteria.

In this study, the effect of three oxidants, sodium hypochlorite, potassium permanganate, and ozone, were tested for the removal of 2-MIB with presence of cyanobacteria. Algae in water samples from the source water of Feng-Shen waterworks (FSW), Taiwan were cultivated at 30 degrees C with continuous light at an intensity between 2,500 and 3,400 lux. During the cultivating process, water samples were analyzed for nutrients, light absorbance at 665 nm (A665), and 2-MIB concentration. The 2-MIB concentrations within the incubated samples increased to as high as 1,000 ng/L to 2,000 ng/L, although no extra nutrients were added to the raw water. After 2 to 3 days incubation, the intracellular 2-MIB concentration was as high as 70% of the total 2-MIB in the samples. The algae that developed were mainly cyanobateria, and more than 90% belonged to the Genus Oscillatorias. An almost 100% removal of both 2-MIB and geosmin in the raw water was observed after ozonation for 10 minutes at a dosing rate of 0.91 mg/l-min. Chlorine and permanganate were much less effective, both removing only about 11% of the 2-MIB within 60 minutes at oxidant concentration of 10 mg/l. Oxidation of the cultivated samples showed that chlorine and permanganate may damage algae cells causing them to release intracellular 2-MIB. During the 60 minutes of reaction time, the total 2-MIB concentrations (intracellular plus dissolved) varied by no more than 10%, however, the ratios between dissolved and total 2-MIB concentrations increased. Two effects of ozonation on the 2-MIB concentration in the cultivated samples were observed when the algae were young, namely 2-MIB release from damaged cells and 2-MIB oxidization. The rates of 2-MIB release and 2-MIB destruction were similar. However, old algae cells were more easily damaged. As a result, intracellular 2-MIB was released faster, and the soluble 2-MIB was destroyed more quickly by ozonation.     

Fenton and photo-Fenton treatment of a synthetic tannin used in leather tannery: a multi-approach study.

The aim of this work was to compare the behaviour of Fenton and photo-Fenton (UV-A, UV-C) processes to treat synthetic tannin (syntan) used in leather tannery which is one of the most polluting industries, releasing many xenobiotics. Both oxidation processes were performed at pH 3.0 and temperature 40-45 degrees C, which is the original temperature of the re-tanning process, in synthetic solutions containing 100 and 300 mg/L of COD equivalent of syntan. The efficiency of the applied oxidation processes was monitored by chemical oxygen demand (COD), oxidation redox potential (ORP) and aromaticity (UV280) and double bond (UV254) absorbance measurements. Acute toxicity test on Daphnia magna was performed to monitor toxicity in untreated and treated syntan solution. Gas chromatography-mass spectrometry (GC-MS) was applied to identify by-products of partial oxidation occurring in treated samples. The effective ratio of H2O2/FeSO4 for photo-Fenton processes was found to be feasible in terms of reagents used in the process.     

水解-气浮-曝气生物滤池工艺在印染废水处理中的应用

采用水解 气浮 曝气生物滤池工艺处理印染废水的运行结果表明 :在原废水COD为830mg/L ,色度为 560倍 ,BOD为 2 90mg/L的条件下 ,其去除率分别为 82 % ,94 %和 93% ,出水达标排放。     

Membrane bioreactor application within the treatment of high-strength textile effluent

A pilot-scale dual-stage membrane bioreactor (dsMBR) incorporating two ultra-filtration (UF) side-stream membrane modules was designed, constructed, operated and evaluated on-site for treating high-strength textile effluent. The effluent stream was characterised by a COD range of between 45 to 2,820 mg/L and an average BOD of 192.5 mg/L. The dsMBR achieved an average COD reduction of 75% with a maximum of 97% over the 9 month test period. The COD concentration obtained after dsMBR treatment averaged at 190 mg/L, which was well within the discharge standard. The average reduction in turbidity and TSS were 94% and 19.6%, respectively, during the UF-MBR stage of the system. Subsequent treatment of the UF-permeate with nanofiltration (NF) and reverse osmosis (RO) removed both the residual colour and remaining salt. A consistent reduction in the color of the incoming effluent was evident. The ADMI was reduced from an average of 659 to ～20, a lower ADMI and colour compared to the potable water. An average conductivity rejection of 91% was achieved with conductivity being reduced from an average of 7,700 to 693 μS/cm and the TDS reduced from an average of 5,700 to 473 mg/L, which facilitated an average TDS rejection of 92%.     

Pre-ozonation in the activated sludge process: fate of nitrogen species

The objective of this research was to include ozonation prior to an activated sludge treatment and investigate the effect on the nitrogen species, their fate and the consequences of this oxidation upon the biomass. Three parallel treatment systems were used: the base system, where feed went directly to the activated sludge reactor, and two others, where the influent was ozonated at two different dosages, 15 and 25 mg/L of influent, prior to the biological reactors. The results from the ozonation chamber show a high oxidation capacity of the entering ammonia and organic nitrogen, proportional to the ozone dose. The oxidation product was nitrate. No de-nitrification was expected because a high oxygen concentration (4 mg/L) was maintained in the reactors. The reactors receiving ozonated influent showed a lower assimilation of nitrogen by the biomass. The sludge nitrogen content resulted in 11, 9.3 and 7.4% dry-weight corresponding to no-ozone, low ozone and high ozone dosages, respectively. In spite of the lower ammonia available in the ozonated flows, the corresponding reactors showed a higher specific nitrification rate. The ozonated system also performed better in terms of chemical oxygen demand (COD) and biochemical oxygen demand (BOD5) removals, besides showing a higher true biomass yield coefficient.