Catalytic wet oxidation of the pretreated synthetic pulp and paper mill effluent under moderate conditions

In the present study, catalytic wet oxidation (CWO) was investigated for the destruction of organic pollutants in the thermally pretreated effluent from a pulp and paper mill under moderate temperature and pressure conditions. The thermal pretreatment studies were conducted at atmospheric pressure and 368K using copper sulfate as a catalyst. The thermal pretreatment reduced COD by about 61%. The filtrate of the thermal pretreatment step was used at pH 8.0 for CWO at 383-443K temperature and a total pressure of 0.85MPa for 4h. Catalysts used for the reaction include copper sulfate, 5% CuO/95% activated carbon, 60% CuO/40% MnO(2), and 60% CuO/40% CeO(2). Maximum COD reduction was found to be 89% during CWO step using 5% CuO/95% activated carbon with a catalyst loading of 8gl(-1) at 443K and 0.85MPa total pressure. Overall COD reduction for the pretreatment and the CWO was found to be 96%. Besides this, 60% CuO/40% CeO(2) catalyst also exhibited the similar activity as that of obtained with 5% CuO/95% activated carbon catalyst at 423K temperature and 0.85MPa total pressure. The pH of the solution during the experimental runs decreases initially due to the formation of carboxylic acid and then increases due to the decomposition of acids.     

Synthetic olive mill wastewater treatment by Fenton’s process in batch and continuous reactors operation

Degradation of total phenol (TPh) and organic matter, (expressed as total organic carbon TOC), of a simulated olive mill wastewater was evaluated by the Fenton oxidation process under batch and continuous mode conditions. A mixture of six phenolic acids usually found in these agro-industrial wastewaters was used for this purpose. The study focused on the optimization of key operational parameters of the Fenton process in a batch reactor, namely Fe²⁺ dosage, hydrogen peroxide concentration, pH, and reaction temperature. On the assessment of the process efficiency, > 99% of TPh and > 56% of TOC removal were attained when [Fe²⁺] = 100 ppm, [H₂O₂] = 2.0 g/L, T = 30 °C, and initial pH = 5.0, after 300 min of reaction. Under those operational conditions, experiments on a continuous stirred-tank reactor (CSTR) were performed for different space-time values (τ). TOC and TPh removals of 47.5 and 96.9%, respectively, were reached at steady-state (for τ = 120 min). High removal of COD (> 75%) and BOD₅ (> 70%) was achieved for both batch and CSTR optimum conditions; analysis of the BOD₅/COD ratio also revealed an increase in the effluent’s biodegradability. Despite the high removal of lumped parameters, the treated effluent did not met the Portuguese legal limits for direct discharge of wastewaters into water bodies, which indicates that coupled chemical-biological process may be the best solution for real olive mill wastewater treatment.     

Coagulation and precipitation as post-treatment of anaerobically treated primary municipal wastewater.

The main objective of this study was to investigate the feasibility of coagulation as a post-treatment method of anaerobically treated primary municipal wastewater. Both mesophilic and ambient (20 degrees C) temperature conditions were investigated in a laboratory-scale upflow anaerobic sludge bed (UASB) reactor. In addition, optimization of the coagulant, both in terms of type and dose, was performed. Finally, phosphorus removal by means of aluminum and iron coagulation and phosphorus and ammonia nitrogen removal by means of struvite precipitation were studied. Anaerobic treatment of primary effluent at low hydraulic retention times (less than 15 hours) resulted in mean chemical oxygen demand (COD) removals ranging from 50 to 70%, while, based on the filtered treated effluent, the mean removals increased to 65 to 80%. Alum coagulation of the UASB effluent gave suspended solids removals ranging from approximately 35 to 65%. Turbidity removal reached up to 80%. Remaining COD values after coagulation and settling were below 100 mg/L, while remaining total organic carbon (TOC) levels were below 50 mg/L. Filterable COD levels were generally below 60 mg/L, while filterable TOC levels were below 40 mg/L. All coagulants tested, including prepolymerized aluminum and iron coagulants, demonstrated similar efficiency compared with alum for the removal of suspended solids, COD, and TOC. Regarding struvite precipitation, optimal conditions for phosphorus and nitrogen removal were pH 10 and molar ratio of magnesium: ammonia-nitrogen: phosphate-phosphorus close to the stoichiometric ratio (1:1:1). During struvite precipitation, removal of suspended solids reached 40%, while turbidity removal reached values up to 80%. The removal of COD was approximately 30 to 35%; yet, when removal of organic matter was based on the treated filterable COD, the removal increased to approximately 65%. In addition, nitrogen was removed by approximately 70%, while phosphorus removal ranged between approximately 30 and 45% on the basis of the initial phosphorus concentration. Finally, size fractionation of the organic matter (COD) showed that the various treatment methods were capable of removing different fractions of the organic matter.     

Electrochemical degradation applied to the metabolites of Acid Orange 7 anaerobic biotreatment

The electrochemical oxidation of the biotic degradation products of the textile dye C.I. Acid Orange 7 (AO7) was achieved using a boron doped diamond electrode (BDD). Tests were performed with model solutions of the biotic degradation products, sulphanilic acid (SA) and 1-amino-2-naphthol (AN), and also with real effluents obtained in experiments carried out in an up-flow anaerobic sludge blanket (UASB) reactor, fed with a simulated textile effluent containing AO7, working in mesophilic or thermophilic conditions. Bulk electrolysis was studied using two different supporting electrolytes - NaCl and Na(2)SO(4). The influence of initial metabolite concentration and current density on the electrodegradation rates of the biotic products was investigated. For the UASB effluents, oxidation tests were carried out for different electrolytes and at different current densities. Samples were collected at pre-selected intervals and absorbance measurements, chemical oxygen demand (COD) and total organic carbon (TOC) tests and high performance liquid chromatography (HPLC) analysis were performed. Results have shown an almost complete elimination of the persistent pollutants and a COD removal higher than 70% for both AN and SA. For the UASB effluents, COD removals between 45% and 90% and TOC removals varying from 19% to 41% were obtained.     

Coal fly ash as adsorptive material for treatment of a real textile effluent: operating parameters and treatment efficiency

The experimental results performed after the application of one single-stage treatment by sorption onto coal fly ash are evaluated in order to decolorize a real textile effluent of a private company specializing in manufacturing of cotton fabrics (i.e., sorption performance applied for a real textile effluent collected after the fabric dyeing, rinsing, and final finishing steps). The experiments are focused on studying the effect of initial textile effluent pH, adsorbent dose, temperature and adsorption time, considered as operating parameters of sorption process for high pollutant removals (e.g., organic pollutants as dyes, phenols, polymeric, and degradation compounds), and decoloration. The results indicate high values of decoloration degree (55.42–83.00 %) and COD removal (44.44–61.11 %) when it is worked at pH ≤2 with coal ash dose of 12–40 g/L, temperature higher than 20–25 °C, and continuous static operating regime (with an initial agitation step of 3–5 min). The treated textile effluent fulfills the quality demand, and is recyclable, inside reused or discharged after a stage of neutralization (standard pH of 6.5–8.5 for all textile effluent discharges). Also, the final effluent is able to follow the common path to the central biological treatment plant (i.e., a centralized treatment plant for all companies acting in the industrial site area with mechanical–biological steps for wastewater treatment) or may be directly discharged in the nearly watercourse.     

Potential of ultrafiltration for organic matter removal in the polymer industry effluent based on particle size distribution analysis

The purpose of the study was the experimental evaluation of ultrafiltration as a potential innovative technology for the removal of organic matter of around 15,000 mg chemical oxygen demand (COD) per liter in the polymer industry wastewater. Particle size distribution (PSD) analysis served as the major experimental instrument along with conventional chemical settling. Biodegradation characteristics of the remaining COD after ultrafiltration were determined by model interpretation of the corresponding oxygen uptake rate (OUR) profile. The study first involved a detailed characterization of the polymer wastewater including PSD analysis of the COD content. Chemical treatability was investigated using lime alone and with ferric chloride as coagulants followed with a PSD assessment of the chemically settled effluent. Modeling of the OUR profile generated by the ultrafiltration effluent defined related biodegradation kinetics and provided information on the overall COD removal potential. PSD analysis indicated that more than 70 % of the total COD accumulated in the 220- to 450-nm size range. It indicated that ultrafiltration was potentially capable of removing more than 90 % of the COD with an effluent lower than 1,500 mg COD/L. Chemical settling with 750 mg/L of FeCl₃ dosing at a pH of 7.0 provided a similar performance. The ultrafiltration effluent included mainly hydrolysable COD and proved to be biodegradable, with the process kinetics compatible with domestic sewage. PSD evaluation proved to be a valuable scientific instrument for underlining the merit of ultrafiltration as the appropriate innovative technology for polymer wastewater, removing the major portion of the COD in a way that is suitable for recovery and reuse and producing a totally biodegradable effluent.     

NaNO(2)/FeCl(3) catalyzed wet oxidation of the azo dye Acid Orange 7

A combination of ferric chloride and sodium nitrite significantly improved the wet oxidation of the azo dye Acid Orange 7 (AO7) in acid aqueous media (pH 2.6) under moderate conditions (T=150 degrees C; oxygen pressure=0.5 MPa). To evaluate the catalytic system, wet oxidation of AO7 was carried out at temperatures between 90 and 150 degrees C and oxygen pressures ranging from 0.1 to 0.5 MPa. The effect of initial solution pH from 2.6 to 11.4 and the amount of catalyst on the degradation of AO7 were also investigated. AO7 initial concentration was kept 200 mg L(-1). The degradation process was monitored by UV-visible spectroscopy, HPLC, IC (ion chromatography), GC-MS and TOC analysis. At 150 degrees C and 0.5 MPa oxygen pressure, 56% TOC was removed after 4h of treatment, while no obvious TOC removal were achieved without catalyst at the same experimental condition. The main degradation products were some small organic acids: formic acid, acetic acid, pyruvic acid, oxalic acid, succinic acid (identified and quantified by IC) and phthalic acid (identified by GC-MS).     

Coupling digestion in a pilot-scale UASB reactor and electrochemical oxidation over BDD anode to treat diluted cheese whey

The efficiency of the anaerobic treatment of cheese whey (CW) at mesophilic conditions was investigated. In addition, the applicability of electrochemical oxidation as an advanced post-treatment for the complete removal of chemical oxygen demand (COD) from the anaerobically treated cheese whey was evaluated. The diluted cheese whey, having a pH of 6.5 and a total COD of 6 g/L, was first treated in a 600-L, pilot-scale up-flow anaerobic sludge blanket (UASB) reactor. The UASB process, which was operated for 87 days at mesophilic conditions (32?±?2 °C) at a hydraulic retention time (HRT) of 3 days, led to a COD removal efficiency between 66 and 97 %, while the particulate matter of the wastewater was effectively removed by entrapment in the sludge blanket of the reactor. When the anaerobic reactor effluent was post-treated over a boron-doped diamond (BDD) anode at 9 and 18 A and in the presence of NaCl as the supporting electrolyte, complete removal of COD was attained after 3–4 h of reaction. During electrochemical experiments, three groups of organochlorinated compounds, namely trihalomethanes (THMs), haloacetonitriles (HANs), and haloketons (HKs), as well as 1,2-dichloroethane (DCA) and chloropicrin were identified as by-products of the process; these, alongside free chlorine, are thought to increase the matrix ecotoxicity to Artemia salina.     

Treatment of pretreated coking wastewater by flocculation,alkali out,air stripping,and three-dimensional electrocatalytic oxidation with parallel plate electrodes

The coking wastewater generally comprises highly concentrated, recalcitrant, and toxic organic pollutants, so its treatment has been of great importance to prevent living beings and their environment from these hazardous contaminations. The treatment of pretreated coking wastewater by flocculation-coagulation, alkali out, air stripping, and three-dimensional (3-D) electrocatalytic oxidation was performed (gap between the used β-PbO₂/Ti anode and titanium cathode, 12 mm; mass ratio of Cu-Mn/granular activated carbon (GAC) to effluent, 1:4; cell voltage, 7 V). The results showed that the pH adjusting from 3.7 to 6.1 was necessary for coagulants; alkali out played an important role because it brought up precipitation containing higher fatty acids as well as other contaminants to decrease the chemical oxygen demand (COD) in the effluent, and it had also forced the reduction of ammonia nitrogen (NH₃-N) by incorporating with air stripping; for 3-D electrocatalytic oxidation with a bleaching liquid assisting, the initial pH 8.5 of effluent was suitable for Cu-Mn/GAC; moreover, it was considered that its Cu component was dedicated to the decrease of COD and NH₃-N, while the Mn component specialized in the decay of NH₃-N. The residual COD and NH₃-N values in the final effluent with pH 6.5 were 95.8 and 8.8 mg/L, respectively, demonstrating that the whole processes applied were feasible and low in cost.     

A novel thermotolerant Pediococcus acidilactici B-25 strain for color, COD, and BOD reduction of distillery effluent for end use applications

The present study was aimed to characterize physico-chemical and microbial population of distillery effluent and isolate a novel thermotolerant bacterium for color, COD, and BOD reduction of spentwash. The level of alkalinity, TSS, DO, COD, BOD, TN, ammonical nitrogen, nitrate nitrogen, phosphorous, potassium, chloride, and calcium of spentwash (SW), bioreactor effluent (BE), and secondary treated effluent (STE) were well above the permissible limits. The level of color, TS, and TDS were under the permissible limits for STE but not for SW and BE. The microbial population was higher in BE. The results revealed that effluent was highly polluted and require suitable treatment before discharge. A novel thermotolerant bacterium, identified as Pediococcus acidilactici, was isolated which exhibited maximum 79 % decolorization, 85 % COD, and 94 % BOD reduction at 45 °C using 0.1 %, glucose; 0.1 %, peptone; 0.05 %, MgSO4; 0.05 %, K₂HPO₄; pH 6.0 within 24 h under static condition. The ability of this strain to decolorize melanoidin at minimum carbon and nitrogen supplementation warrants its possible application for effluent treatment at industrial level. In addition, it is first instance when melanoidin decolorization was reported by P. acidilactici. This study could be an approach towards control of environmental pollution and health hazards of people in and around the effluent distillery unit.     

Co-treatment of acid mine drainage with municipal wastewater: performance evaluation

Co-treatment of acid mine drainage (AMD) with municipal wastewater (MWW) using the activated sludge process is a novel treatment technology offering potential savings over alternative systems in materials, proprietary chemicals and energy inputs. The impacts of AMD on laboratory-scale activated sludge units (plug-flow and sequencing batch reactors) treating synthetic MWW were investigated. Synthetic AMD containing Al, Cu, Fe, Mn, Pb, Zn and SO₄ at a range of concentrations and pH values was formulated to simulate three possible co-treatment processes, i.e., (1) adding raw AMD to the activated sludge aeration tank, (2) pre-treating AMD prior to adding to the aeration tank by mixing with digested sludge and (3) pre-treating AMD by mixing with screened MWW. Continuous AMD loading to the activated sludge reactors during co-treatment did not cause a significant decrease in chemical oxygen demand (COD), 5-day biochemical oxygen demand, or total organic carbon removal; average COD removal rates ranged from 87–93 %. Enhanced phosphate removal was observed in reactors loaded with Fe- and Al-rich AMD, with final effluent TP concentrations <2 mg/L. Removal rates for dissolved Al, Cu, Fe and Pb were 52–84 %, 47–61 %, 74–86 % and 100 %, respectively, in both systems. Manganese and Zn removal were strongly linked to acidity; removal from net-acidic AMD was <10 % for both metals, whereas removal from circum-neutral AMD averaged 93–95 % for Mn and 58–90 % for Zn. Pre-mixing with screened MWW was the best process option in terms of AMD neutralization and metal removal. However, significant MWW alkalinity was consumed, suggesting an alkali supplement may be necessary.     

Hydraulic residence time effects on performance of an activated sludge unit treating wastewater containing dichlorophenol.

Wastewaters containing chlorophenol compounds are difficult to treat by biological means because of the toxic effects of those compounds on microorganisms. To investigate the adverse effects of chlorophenols on microorganisms, synthetic wastewater containing 2,4 dichlorophenol (DCP) was biologically treated in an activated sludge unit at different hydraulic residence times (HRTs) between 5 and 40 hours, whereas the feed chemical oxygen demand (COD), DCP concentrations, and sludge age were kept constant at 2500 +/- 50 mg/L, 150 mg/L, and 20 days, respectively. The resazurin method based on dehydrogenase activity was used for assessment of the feed and effluent wastewater toxicity. Percent COD, DCP, and toxicity removals increased, and the effluent COD, DCP, and toxicity levels decreased with increasing HRT. Biomass concentration in the aeration tank increased with increasing HRT because of low levels of DCP at high HRT levels, resulting in high COD, DCP, and toxicity removals. The sludge volume index decreased with increasing HRT, yielding well-settling organisms as a result of low levels of toxicity and high concentrations of active cells. Percent DCP and COD removals decreased with increasing specific DCP loading rate. The rates of DCP and COD removals showed a maximum at a low DCP concentration of 6 mg/L in the aeration tank, corresponding to a 25-hour HRT.     

Sonochemical degradation of a pharmaceutical waste,atenolol, in aqueous medium

Atenolol is a β-blocker drug and an identified emerging pollutant. Advanced oxidation processes (AOPs) utilise the reaction of a highly oxidising species (hydroxyl radicals, ^?OH) for the mineralisation of emerging pollutants since conventional treatment methodologies generally fail to degrade these compounds. In the present work, degradation of atenolol was carried out using ultrasound with frequencies ranging from 200 kHz to 1 MHz as a source of hydroxyl radical. The degradation was monitored by HPLC, total organic carbon (TOC) and chemical oxygen demand (COD) reduction and ion chromatography (IC). Nearly 90 % of degradation of atenolol was observed with ultrasound having 350 kHz. Both frequency and power of ultrasound affect the efficiency of degradation. Nearly 100 % degradation was obtained at a pH of 4. Presence of various additives such as sodium dodecyl sulphate, chloride, sulphate, nitrate, phosphate and bicarbonate was found to reduce the efficiency of degradation. Although nearly 100 % degradation of atenolol was observed under various experimental conditions, only about 62 % mineralisation (from TOC and COD measurements) was obtained. Nearly eight intermediate products were identified using high-resolution mass spectrometry (LC-Q-TOF). These products were understood as the results of hydroxyl radical addition to atenolol. The degradation studies were also carried out in river water which also showed a similar degradation profile. A mechanism of degradation and mineralisation is presented.     

Impacts of COD and DCP loading rates on biological treatment of 2,4-dichlorophenol (DCP) containing wastewater in a perforated tubes biofilm reactor

Biofilm processes offer considerable advantages for biological treatment of chlorophenol containing wastewaters since such industrial effluents are difficult to treat by conventional activated sludge processes. A rotating perforated tubes biofilm reactor (RTBR) was developed and used for treatment of 2,4-dichlorophenol (DCP) containing synthetic wastewater. Effects of COD and DCP loading rates on COD, DCP and toxicity removals were investigated. Percent COD removal decreased and effluent COD increased with increasing COD and DCP loading rates due to toxic effects of high DCP content in the feed. DCP and toxicity removals showed similar trends. As the DCP loading rate increased the effluent DCP content increased yielding high toxicity levels in the effluent. COD and DCP loading rates should be below 90gCODm(-2)d(-1) and 2.8gDCPm(-2)d(-1) in order to obtain more than 90% DCP and toxicity removals. However, DCP loading rates lower than 1gDCPm(-2)d(-1) are required to obtain more than 90% COD removal. Empirical equations were developed to estimate percent COD, DCP and toxicity removals as functions of COD and DCP loading rates. The coefficients of the empirical equations were determined by using the experimental data. Empirical model predictions for percent COD, DCP and toxicity removals were in good agreement with the experimental data.     

Application of the Fenton’s process in a bubble column reactor for hydroquinone degradation

The aim of this study was to assess the degradation and mineralization of hydroquinone (HQ) by the Fenton’s process in a bubble column reactor (BCR). The effect of the main operating variables, namely, air flow rate, effluent volume, hydrogen peroxide (H₂O₂) concentration, catalyst (Fe²⁺) dose, initial pH, and temperature, were assessed. For all air flow rates tested, no concentration gradients along the column were noticed, evidencing that a good mixing was reached in the BCR. For the best conditions tested ([H₂O₂] = 500 mg/L, [Fe²⁺] = 45 mg/L, T = 24 °C, Q _air = 2.5 mL/min, pH = 3.0, and V = 5 L), complete HQ degradation was reached, with ~ 39% of total organic carbon (TOC) removal, and an efficiency of the oxidant use—η _H2O2—of 0.39 (ratio between TOC removed per H₂O₂ consumed normalized by the theoretical stoichiometric value); moreover, a non-toxic effluent was generated. Under these conditions, the intermediates and final oxidation compounds identified and quantified were a few carboxylic acids, namely, maleic, pyruvic, and oxalic. As a strategy to improve the TOC removal, a gradual dosage of the optimal H₂O₂ concentration was implemented, being obtained ~ 55% of mineralization (with complete HQ degradation). Finally, the matrix effect was evaluated, for which a real wastewater was spiked with 100 mg/L of HQ; no reduction in terms of HQ degradation and mineralization was observed compared to the solution in distilled water.     

An assessment of the suitable operating conditions for the CeO2/gamma-Al2O3 catalyzed wet air oxidation of phenol

It has been shown that the CeO2/gamma-Al2O3 catalyst is a feasible alternative to CeO2 for the catalytic wet air oxidation (CWAO) of phenol because it remains an effective catalyst and yet is cheaper to prepare. In this study, we found that the optimal cerium content in the CeO2/gamma-Al2O3 catalyst was 20 wt.%, regardless of catalyst loading. Furthermore, at 180 degrees C, with a phenol concentration of 1000 mg l(-1), and an O2 partial pressure of 1.0M Pa or 1.5M Pa, the optimal catalyst loading was 3.0 gl (-1). The efficacy of CWAO of phenol improved with O2 partial pressure, although the effects of O2 pressure were more significant between 0.5 MPa and 1.5 MPa than between 1.5 MPa and 2.0 MPa. After 2 h of reaction, approximately 100% phenol conversion and 80% total organic carbon (TOC) removal was recorded at 180 degrees C, 1000 mg l(-1) of phenol and 3.0 g l(-1) of catalyst. Because these percentages subsequently leveled off, it is suggested that 2 h is a suitable time over which to run the reaction. The efficacy of CWAO of phenol decreased as initial phenol concentration was raised (from 400 to 2500 mg l(-1)), with the exception of phenol conversion after about 2 h, for which 400 mg l(-1) produced the lowest phenol conversion figure. Higher phenol concentrations require both catalyst loading and O2 partial pressure to be increased to maintain high performance. For example, for 2000 mg l(-1) and 2500 mg l(-1) phenol, nearly 100% phenol conversion and 90% TOC removal after 4 h of reaction at 180 degrees C required 4.0 g l(-1) of catalyst and 2.0 MPa.     

Low-pressure catalytic wet-air oxidation of a high-strength industrial wastewater using Fenton's reagent.

Wastewater from the Afyon Alkaloids Factory (Afyon, Turkey) was subjected to low-pressure catalytic wet-air oxidation (CWAO) using Fenton's reagent, and the optimal reaction conditions were investigated. The CWAO using Fenton's reagent was applied to the factory effluent, diluted factory effluent, and aerobically pretreated wastewater. To find the optimum quantities of reagents, ferrous iron (Fe(+2))-to-substrate ratios of 1:10, 1:25, and 1:50 and hydrogen peroxide (H2O2)-to-Fe(+2) ratios of 1, 5, and 10 were investigated, and the treatment was carried out at different temperatures. High chemical oxygen demand (COD) removals were obtained at 50 degrees C, with the Fe(+2)-to-substrate ratio range between 1:10 and 1:25. The change in H2O2-to-Fe(+2) ratios did not cause any considerable effect. Also, the percentages of COD removals were nearly the same, so the ratio H2O2:Fe(+2):1 is recommended. Aerobic pretreatment seems to be effective. On the other hand, no enhancement was observed in the case of the diluted wastewater.     

Petroleum refinery secondary effluent polishing using freezing processes--toxicity and organic contaminant removal

A petroleum refinery secondary effluent was treated using two freezing techniques--spray freezing and unidirectional downward freezing (UDF). The freezing processes were effective to remove toxicity and total organic carbon (TOC)- and chemical oxygen demand (COD)-causing materials in the effluent. Agitation of the liquid during UDF significantly improved the impurity separation efficiency; 85 to 96% removal of TOC and COD was achieved without any pretreatment and freezing only 70% of the feed water. The treatment efficiency of the spray freezing was at the same level as that of UDF without mixing. The spray ice with longer storage time released more contaminants with early meltwater. The initial contaminant concentration of the feed water and the freezing temperatures (-10 degrees C and -25 degrees C) had no significant influence on the treatment efficiency. A small fluctuation in effluent TOC concentration caused a dramatic change in effluent toxicity (Microtox). The effective concentration (EC20) (Microtox) was effective in detecting effluent toxicity.     

Electro-Fenton pretreatment for the improvement of tylosin biodegradability

The feasibility of an electro-Fenton process to treat tylosin (TYL), a non-biodegradable antibiotic, was examined in a discontinuous electrochemical cell with divided cathodic and anodic compartments. Only 15 min electrolysis was needed for total tylosin degradation using a carbon felt cathode and a platinum anode; while 6 h electrolysis was needed to achieve high oxidation and mineralization yields, 96 and 88 % respectively. Biodegradability improvement was shown since BOD₅/COD increased from 0 initially to 0.6 after 6 h electrolysis (for 100 mg L^?1 initial TYL). With the aim of combining electro-Fenton with a biological treatment, an oxidation time in the range 2 to 4 h has been however considered. Results of AOS (average oxidation state) and COD/TOC suggested that the pretreatment could be stopped after 2 h rather than 4 h; while in the same time, the increase of biodegradability between 2 and 4 h suggested that this latter duration seemed more appropriate. In order to conclude, biological cultures have been therefore carried out for various electrolysis times. TYL solutions electrolyzed during 2 and 4 h were then treated with activated sludge during 25 days, showing 57 and 67 % total organic carbon (TOC) removal, respectively, namely 77 and 88 % overall TOC removal if both processes were considered. Activated sludge cultures appeared, therefore, in agreement with the assessment made from the analysis of physico-chemical parameters (AOS and COD/TOC), since the gain in terms of mineralization expected from increasing electrolysis duration appeared too low to balance the additional energy consumption.     

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.