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.     

Treatment of an ECF effluent by combined use of activated sludge and advanced oxidation process.

The combined biological and chemical treatments of the cellulose effluents have been studied aiming to promote a more significant degradation of their recalcitrant compounds and to reduce their toxicity, as compared with the isolated treatments. In this work the effluent from acid stages of the ECF bleaching of Eucalyptus urograndis pulp was treated by using separately activated sludge and UV radiation and its combination. The treatment efficiency was evaluated by colour, total phenol, COD, BOD, UV spectroscopy, molar weight distribution and toxicity. The untreated effluent presented 587 +/- 18 CU, 19.3 +/- 0.6 mg.L(-1) of total phenol, 2246 +/- 137 mgO2.L(-1) of COD and 904 +/- 48 mgO2.L(-1) of BOD. It did not show acute toxicity to Escherichia coli, but presented chronic toxicity to Selenastrum capricornutum (EC50 = 25%). The sludge treatment resulted in a colour increasing of 42% and decreasing of total phenol, COD and BOD of 33%, 64% and 92%, respectively. The UV radiation treatment for 120 min resulted in a decrease of colour, total phenol, BOD and COD of 70%, 43%, 62% and 43%, respectively. The combined treatment promoted an expressive decrease for colour and total phenol. The UV absorption indicated a degradation of the aromatic compounds. The biological treatment did not remove chronic toxicity and after UV radiation treatment, a 10 times improving toxicity was noticed.     

Using ozone to reduce recalcitrant compounds and to enhance biodegradability of pulp and paper effluents.

The effect of ozone based oxidation on removing recalcitrant organic matter (ROM) and enhancing the biodegradability of alkaline bleach plant effluent was investigated. A bubble column ozonation tower was used in the study. The experiments were carried out at different temperatures (20 degrees C and 60 degrees C) and pH (9 and 11), with a number of biological and chemical parameters being monitored including BOD5, COD, TC, pH, color, and molecular weight distribution of organics (nominal cut off of 1,000 Da). Biodegradability of the effluent was determined based on BOD5/COD of the wastewater throughout the process. For all the experiments, ozonation enhanced the biodegradability of the effluent by 30-40%, which was associated with noticeable removal of ROM including high molecular weight (HMW) and color-causing organics by about 30% and 60%, respectively. While the biodegradability of HMW fraction increased by about 50%, there was no biodegradability improvement for low molecular weight (LMW) portion, which was originally readily biodegradable (with BOD5/COD of about 0.5). Statistical analysis of variance (ANOVA) revealed neither pH nor temperature played significant role on the ozonation process at 95% confidence level.     

Optimization of Fenton process for decoloration and COD removal in tobacco wastewater and toxicological evaluation of the effluent

Decoloration and chemical oxygen demand (COD) removal in tobacco wastewater by Fenton process has been optimized under 25 +/- 2 degrees C. The results showed that the optimal range of conditions were pH 4.13-4.66, Fe(2+) 0.29-0.34 g/L and H2O2 > or = 2.73 g/L. Within this range, up to 95% of colour and 90% of COD was removed. In an enlarged system, setting the optimal conditions as pH 4.50, Fe(2+) 0.34 g/L and H2O2 4.00 g/L, the colour removal rate was 96.03 +/- 2.57%, with COD removal rate of 93.30 +/- 2.92%. The residual COD of 73.67 +/- 19.70 mg/L in effluent had hit the State's first-class standard for the industrial discharge in China (< 100 mg/L COD, GB8978-1996). The ecological safety of Fenton process has also been evaluated. When reaction completed, the content of hydroxyl free radical (OH) was 3.26 +/- 0.44 mg/L. There was no inhibition of Fenton effluent in growth of Escherichia coli, Pseudomonas putida, Pseudomonas sp. HF-1, Acinetobacter sp. TW and Sphingomonas sp. TY. No oxidative stress was induced on strain HF-1 by Fenton effluent. Thus, Fenton process was one of high-efficiency and ecologically safe strategy for tobacco wastewater advanced treatment.     

Leachate detoxification by combination of biological and TiO2-photocatalytic processes.

Landfill leachates are a problematic wastewater due to their variable concentration, volume changing in time and presence of refractory and hazardous components. In this paper, the results of a new approach to photocatalysis assisted by biological process for the detoxification of stabilised landfill leachate are presented. The biologically pre-treated leachate still contained a significant amount of non-biodegradable COD and TOC amounting to 500 and 200 mg/L, respectively. The 300 min of photocatalytic treatment (UVC/TiO2) brought about a significant decrease in more than 80% refractory organics remaining in leachate. The effect of pH and catalyst loading on mineralisation, colour removal rate and biodegradability (BOD/COD) improvement in the photoreactor were discussed. The bio-accessibility of formed photocatalytic oxidation intermediates was confirmed by oxygen uptake rate (OUR) measurements. Consequently, a part of COD was successfully removed in post-biological treatment.     

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.     

Treatment of industrial wastewater using photooxidation and bioaugmentation technology.

The versatile metabolism of microorganisms has an played important role in the biodegradation of recalcitrant toxic compounds entering into the natural environment. The biodegradability of organics can be enhanced using bioaugmentation and advanced oxidation processes (AOP) for aerobic/anaerobic treatment programs. Wastewater from a bulk drug (cresol) plant had high levels of TDS, COD and BOD, whilst the levels from a pigment plant low. Both contained organics difficult to degrade. AOP using hydroxyl radical generated in 1 L glass reactor using UV and H2O2 efficiently oxidised phenol and cresol. COD and sulphite reduction in cresol containing wastewater were 20-60% in 1-6 h. A twenty to thirty percent reduction in copper phthalocyanine pigment effluents was achieved in 6 h using AOP. Strains of Micrococcus, Pseudomonas, and Nocardia degrading phenol, cresol were isolated from soil and sludge. Mixed biomass of these organisms removed phenols (1,000 ppm) and cresols (500 ppm) completely in 24 and 72 h, respectively. The COD and BOD reductions under the optimum nutritional and physiological conditions were in the range of 70 to 90%. When added to the bioreactor, 20% of the developed biomass of mixed strains of Micrococcus, Nocardia and Pseudomonas increased the rate of COD and BOD reduction gradually and stabilised at 80-90%. Added biomass improved the overall efficiency of the aerobic process.     

Anaerobic treatment of Hong Kong leachate followed by chemical oxidation.

Landfill leachate of Hong Kong was first treated by the upflow anaerobic sludge blanket (UASB) process. At 37 degrees C, pH 7.1-8.5 and a HRT of 5.1-6.6 days, the process removed 66-90% of COD in the leachate for loading rates of 1-2.4 g-COD/l day depending on the strength of landfill leachate. The final effluent contained 1440-1910 mg-COD/l and 70-91 mg-BOD/l. About 92.5% of the total COD removed was converted to methane and the rest was converted to biomass with an average net growth yield of 0.053 g-VSS/g-COD-removed. The granules developed in the UASB reactor were 0.5-1.5 mm in size and exhibited good settleability. The UASB effluent was then further polished by two oxidation processes. The UASB-ozonation process removed 93.0% of the 12900 mg/l of COD from the raw leachate. The UASB-Fenton-ozonation process improved the COD removal efficiency to 99.3%. The final effluent had only 85 mg/l of COD and 10 mg/l of BOD5. Ozonation was most effectively conducted at pH 7-8 with the addition of 300 mg/l of H2O2 and for the duration of 30 min. Ozonation also significantly improved the biodegradability of the organic residues. Nearly 50% of these residues could be used as carbon source in denitrification.     

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.     

Biodegradability enhancement of municipal landfill leachate

The method of enhancing the biodegradability of landfill leachate via air stripping followed by coagulation/ultrafiltration （UF） processes is introduced. In this study, the air stripping process obtained a removal efficiency of 88.6% for ammonia nitrogen （NH3-N）, at an air-to-liquid ratio （A/L） of 3 300 （pH = 11） and after 18 h of stripping. The single coagulation process increased the BOD （biological oxygen demand）/COD （chemical oxygen demand） ratio by 0.089 with a FeCl3 dosage of 570 mg/L, at pH 7.0, and the single UF process increased the BOD/COD ratio from 0.049 to 0.311. However, the combination of coagulation and UF increased the BOD/COD ratio from 0.049 to 0.423, and the final BOD, COD, NH3-N, and colour of the leachate were 1 023 mg/L, 2 845 mg/L, 145 mg/L, and 2 056, respectively, when a 3 kDa molecular weight cut-off （MWCO） membrane was used at an operating pressure of 0.7 MPa. In the ultrafiltration process, the average solution flux （Jv）, concentration multiple （Mc）, and retention rate （R） for the COD were 107.3 L/（m^2·h）, 6.3, and 84.2%, respectively.     

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.     

Electrolytic degradation of biorefractory organics and ammonia in leachate from bioreactor landfill.

Electrochemical oxidation was applied to treat the effluent from bioreactor landfill with leachate recirculation, characterised as poor biodegradability and high NH3-N concentration. In this study, the effluent was electrolysed in a batch reactor with Ti/TiO2-IrO2-RuO2 anode and stainless steel cathode. The oxidation of dissolved organic matter (DOM) during electrolysis was evaluated based on the evolution of molecular weight grade, hydrophilic fractionation (humic acid, fulvic acid and hydrophilic fractions), specific ultraviolet absorbance (SUVA254) and AOX. The impact of the initial NH3-N concentration on the oxidation was discussed. The results showed that at a current density of 100 mA/cm2, electrolysis time of 1.5 h and electrode gap of 1 cm, NH3-N with an initial concentration of 1.2 g/L could be completely eliminated and 56% of COD with an initial concentration of 1.2 g/L could be removed, which illustrated that the electrolysis-produced chlorine preferentially oxidised ammonia. The electrolysis mainly resulted in the degradation of humic substances and other high molecular DOM, followed by the increase of BOD/COD ratio and decline of SUVA254 of the leachate. The current efficiencies for COD and ammonia oxidation gradually decreased during the electrolysis, with the latter obviously higher than the former. At the optimal electrolysis time of 1.5 h, NH3-N could be totally removed and the BOD/COD ratio could be enhanced to 0.3, which was also favourable to control the AOX at a reasonable level.     

H_2O_2与沸石联用处理污水厂二级出水的研究

为探寻污水厂二级出水深度处理方法,以阜新市某污水处理公司二级出水为研究对象,进行H2O2与沸石联用去除水中COD、氨氮的研究。结果表明：在二氧化锰的催化作用下,pH值为7时,H2O2和沸石的投加量分别为1.5mL和2g,二级出水的COD从138.24mg/L降到52.76mg/L,去除率达到75.36%,NH3-N从20mg/L降到5mg/L,去除率为74.59%,出水有机物和氨氮含量达到国家相关出水标准。     

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 recirculation on organic matter removal in a hybrid constructed wetland system

This research project aimed to determine the technologically feasible and applicable wastewater treatment systems which will be constructed to solve environmental problems caused by small communities in Turkey. Pilot-scale treatment of a small community's wastewater was performed over a period of more than 2 years in order to show applicability of these systems. The present study involves removal of organic matter and suspended solids in serially operated horizontal (HFCW) and vertical (VFCW) sub-surface flow constructed wetlands. The pilot-scale wetland was constructed downstream of anaerobic reactors at the campus of TUBITAK-MRC. Anaerobically pretreated wastewater was introduced into this hybrid two-stage sub-surface flow wetland system (TSCW). Wastewater was first introduced into the horizontal sub-surface flow system and then the vertical flow system before being discharged. Recirculation of the effluent was tested in the system. When the recirculation ratio was 100%, average removal efficiencies for TSCW were 91 +/- 4% for COD, 83 +/- 10% for BOD and 96 +/- 3% for suspended solids with average effluent concentrations of 9 +/- 5 mg/L COD, 6 +/- 3 mg/L BOD and 1 mg/L for suspended solids. Comparing non-recirculation and recirculation periods, the lowest effluent concentrations were obtained with a 100% recirculation ratio. The effluent concentrations met the Turkish regulations for discharge limits of COD, BOD and TSS in each case. The study showed that a hybrid constructed wetland system with recirculation is a very effective method of obtaining very low effluent organic matter and suspended solids concentrations downstream of anaerobic pretreatment of domestic wastewaters in small communities.     

Combining photo-Fenton process with biological sequencing batch reactor for 2,4-dichlorophenol degradation.

The effect of the photo-Fenton process on biodegradability enhancement of 100 mg x L(-1) aqueous 2,4-dichlorophenol (2,4-DCP) solution has been investigated. An initial concentration of 65 mg x L(-1) H2O2 and 10 mg x L(-1) Fe (II) during 35 minutes of irradiation time was sufficient for total 2,4-DCP removal. At these working conditions, biodegradability, measured as BODS/COD ratio, was increased from 0 for the original solution up to 0.15. Biological oxidation of photo-Fenton pre-treated solutions was performed in a sequencing batch reactor (SBR). After 32 days of start-up, the reactor was fed with different pre-treated solutions and cycle duration was reduced progressively. TOC removal efficiencies in the SBR went from 30 up to 70%.     

Increasing the capacity for treatment of chemical plant wastewater by replacing existing suspended carrier media with Kaldnes Moving Bed media at a plant in Singapore.

The Kaldnes biomedia K1, which is used in the patented Kaldnes Moving Bed biofilm process, has been tested along with other types of biofilm carriers for biological pretreatment of a complex chemical industry wastewater. The main objective of the test was to find a biofilm carrier that could replace the existing suspended carrier media and at the same time increase the capacity of the existing roughing filter-activated sludge plant by 20% or more. At volumetric organic loads of 7.1 kg COD/m3/d the Kaldnes Moving Bed process achieved much higher removal rates and much lower effluent concentrations than roughing filters using other carriers. The Kaldnes roughing stage achieved more than 85% removal of organic carbon and more than 90% removal of BOD5 at the tested organic load, which was equivalent to a specific biofilm surface area load of 24 g COD/m2/d. Even for the combined roughing filter-activated sludge process, the Kaldnes carriers outperformed the other carriers, with 98% removal of organic carbon and 99.6% removal of BOD5. The Kaldnes train final effluent concentrations were only 22 mg FOC/L and 7 mg BOD5/L. Based on the successful pilot testing, the full-scale plant was upgraded with Kaldnes Moving Bed roughing filters. During normal operation the upgraded plant has easily met the discharge limits of 100 mg COD/L and 50 mg SS/L. For the month of September 2002, with organic loads between 100 and 115% of the design load for the second half of the month, average effluent concentrations were as low as 9 mg FOC/L, 51 mg COD/L and 12 mg SS/L.     

Photocatalytical polishing of paper-mill effluents.

Photocatalytic oxidation (PCO) is a promising technology for purification of biological pretreated wastewater or destruction of non-biodegradable compounds. For this reason PCO has been investigated as a last step of purification of biologically pre-treated paper-mill effluents. The influence of the parameters pH, TiO2-modification, TiO2-concentration, catalyst re-use, concentration of substances to be oxidised (wastewater quality) has been determined. The TOC of the biologically pretreated wasterwater was up to 55 mg L(-1). This wastewater was treated with a previously presented aerated cascade photoreactor which was modified for batch experiments. A high specific oxidation rate of up to 0.76 g TOC m(-2) h(-1) as well as a complete TOC mineralization has been achieved after the optimisation of the process parameters. The complete destruction of recalcitrant compounds will offer the opportunity to reuse the wastewater in the production process. The increase of the BOD5/TOC ratio after a short irradiation period indicates the transformation of recalcitrant organic compounds to better biodegradable intermediates. The use of PCO as a pre-treatment step for the enhancement of the biodegradability of wastewater, containing recalcitrant or inhibitory compounds is an alternative to a long and energy-intensive total pollutant mineralization.     

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.     

Effect of hot acid hydrolysis and hot chlorine dioxide stage on bleaching effluent biodegradability.

The hot acid hydrolysis followed by chlorine dioxide (A/D*) and hot chlorine dioxide (D*) technologies have proven very useful for bleaching of eucalyptus kraft pulp. Although the characteristics and biodegradability of effluents from conventional chlorine dioxide bleaching are well known, such information is not yet available for effluents derived from hot acid hydrolysis and hot chorine dioxide bleaching. This study discusses the characteristics and biodegradability of such effluents. Combined whole effluents from the complete sequences DEpD, D*EpD, A/D*EpD and ADEpD, and from the pre-bleaching sequences DEp, D*Ep, A/D*Ep and ADEp were characterized by quantifying their colour, AOX and organic load (BOD, COD, TOC). These effluents were also evaluated for their treatability by simulation of an activated sludge system. It was concluded that treatment in the laboratory sequencing batch reactor was efficient for removal of COD, BOD and TOC of all effluents. However, colour increased after biological treatment, with the greatest increase found for the effluent produced using the AD technology. Biological treatment was less efficient at removing AOX of effluents from the sequences with D*, A/D* and AD as the first stages, when compared to the reference D stage; there was evidence of the lower treatability of these organochlorine compounds from these sequences.