Mineralization of some natural refractory organic compounds by biodegradation and ozonation

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

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

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

The effect of operational parameters of the process of sludge ozonation on the solubilisation of organic and nitrogenous compounds

An evaluation of various operational parameters on the process of sludge ozonation was carried out based on semi-batch experiments. Particular reference has been given to examine the main parameters affecting the solubilisation of organic matter and nitrogenous compounds. Various sets of experiments were undertaken using real sewage sludge to feed a semi-industrial ozonation plant. Applying ozone dosages between 25 and 35 mg O(3)/gTSS, the organic matter solubilisation obtained through ozonation increases proportionally to ozone dosage until a maximum value of 430 mg COD/L. Concerning the nitrogenous compounds, no variation in nitrite concentration and a low increase in nitrate concentration were attained, regardless of the applied ozone dosage. Little increase in ammonia concentration was achieved for low ozone dosages, whilst applying dosages higher than 20 mg O(3)/gTSS, the variation of ammonia increased proportionally with ozone dosage. Experiments using hydraulic retention time (HRT) between 10 and 60 min resulted in a similar COD solubilisation, confirming a rapid rate of cell lysis during ozonation of sludge.     

Combined chemical and biological degradation of tannery wastewater by a periodic submerged filter (SBBR)

The paper reports on the results of an investigation aimed to evaluate the performances of an innovative tannery wastewater process based on the combining biological degradation, carried out in a sequencing batch biofilm reactor, with chemical oxidation, performed by ozone. The combined treatment was carried out at the laboratory scale on real primary effluent coming from a centralised plant treating the wastewater from a large tanning district in Northern Italy. SBBR performances with and without ozonation were compared resulting to be very satisfactory only in the latter instance where recorded COD, NH4-N and TSS average removals were 97%, 98% and 99.9%, respectively. Such efficiencies correspond to specific concentrations in treated effluent well below the limit values fixed by the in-force Italian regulations. Furthermore, it was proved that the combined process is characterised by a very low sludge production. In fact, the measured specific sludge production (0.03 kg TSS/kg COD(removed)) resulted unexpectedly much more lower than the value reported for conventional biological systems (i.e., 0.3-0.5 kg TSS/kg COD(removed)).     

Comparative study of laboratory-scale thermophilic and mesophilic activated sludge processes

Laboratory-scale mesophilic (20-35 degrees C) and thermophilic (55 degrees C) activated sludge processes (ASPs) treating diluted molasses wastewater were compared in effluent quality, removal of different COD fractions, sludge yield, floc size, and sludge settleability. The effect of polyaluminium chloride (PAC) with high cationic charge on sludge settleability and effluent quality was also studied. In the ASPs, the hydraulic retention time was 12h in both processes, corresponding to a volumetric loading rate of 3.2+/-1.0 kg COD(filt) m(-3)d(-1). The mesophilic ASP gave 79+/-18% and 90+/-2% and the thermophilic ASP gave 50+/-6% and 67+/-11% total COD (COD(tot)) and GF/A-filtered COD (COD(filt)) removals, respectively. The higher COD values in the thermophilic effluent were due to dispersed particles, such as free bacteria, measured as colloidal COD (COD(col)=difference between soluble COD (COD(sol)) and COD(filt)). Both ASPs gave high (90%) COD(sol) removals. Aeration (24-h) of the thermophilic ASP effluent at 35 degrees C reduced the density of the free bacteria by half, which was also measured as 90% COD(col) removal. Post-aeration of thermophilic effluent at 55 degrees C had no influence either on the density of free bacteria or on the COD(col) values. The use of PAC did not increase COD(tot) or COD(filt) removals in either process, but reduced the mesophilic and increased the thermophilic sludge volume index values.     

Effects of ozone pre-treatment on diclofenac: Intermediates, biodegradability and toxicity assessment

Diclofenac (DCF), a common analgesic, anti-arthritic and anti-rheumatic drug, is one of the most frequently detected compounds in water. This study deals with the degradation of diclofenac in aqueous solution by ozonation. Biodegradability (BOD₅/COD ratio and Zahn-Wellens test), acute ecotoxicity and inhibition of activated sludge activity were determined in ozonated and non-ozonated samples. Liquid chromatography coupled with time-of-flight mass spectrometry (LC/TOF-MS) was used to identify the intermediates formed in 1 h of ozonation. Eighteen intermediates were identified by these techniques and a tentative degradation pathway for DCF ozonation is proposed.Experimental results show that ozone is efficient at removing DCF: > 99% removal (starting from an initial concentration of 0.68 mmol L^− 1) was achieved after 30 min of ozonation (corresponding to an absorbed ozone dose of 0.22 g L^− 1, which is 4.58 mmol L^− 1). However, only 24% of the substrate was mineralized after 1 h of ozonation. The biodegradability, respiration inhibition in activated sludge and acute toxicity tests demonstrate that ozonation promotes a more biocompatible effluent of waters containing DCF.     

Nitrogen control in AO process with recirculation of solubilized excess sludge

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

Ozonation reduces sludge production and improves denitrification

The effectiveness of partial ozonation of return activated sludge for enhancing denitrification and waste sludge minimization were examined. A pair of nitrifying sequencing batch reactors was operated in either aerobic or alternating anoxic/aerobic conditions, with one control and one ozonated reactor in each set. The amount of solids produced decreased with the ozone dose. Biomass in the anoxic/aerobic reactor was easier to destroy (up to 25% of the initial excess sludge) than in the aerobic (10%) one, generating approximately twice as much soluble COD by cell lysis. Denitrification rate improved up to 60% due to additional carbon released by ozonation. Nitrification rates deteriorated much more in the aerobic than in the alternating reactor, possibly as a result of direct destruction of nitrifying autotrophs as well as competition created by growth of heterotrophs receiving the additional COD. Overall, ozonation provided the expected benefits in denitrification and had less impact on nitrification in the alternating reactors.     

Biomass characteristics in three sequencing batch reactors treating a wastewater containing synthetic organic chemicals

The physical and biochemical characteristics of the biomass in three lab-scale sequencing batch reactors (SBR) treating a synthetic wastewater at a 20-day target solids retention time (SRT) were investigated. The synthetic wastewater feed contained biogenic compounds and 22 organic priming compounds, chosen to represent a wide variety of chemical structures with different N, P and S functional groups. At a two-day hydraulic retention time (HRT), the oxidation-reduction potential (ORP) cycled between -100 (anoxic) and 100 mV (aerobic) in the anoxic/aerobic SBR, while it remained in a range of 126+/-18 and 249+/-18 mV in the aerobic sequencing batch biofilm reactor (SBBR) and the aerobic SBR reactor, respectively. A granular activated sludge with excellent settleability (SVI=98+/-31 L mg(-1)) developed only in the anoxic/aerobic SBR, compared to a bulky sludge with poor settling characteristics in the aerobic SBR and SBBR. While all reactors had very good COD removal (>90%) and displayed nitrification, substantial nitrogen removal (74%) was only achieved in the anoxic/aerobic SBR. During the entire operational period, benzoate, theophylline and 4-chlorophenol were completely removed in all reactors. In contrast, effluent 3-nitrobenzoate was recorded when its influent concentration was increased to 5 mg L(-1) and dropped only to below 1 mg L(-1) after 300 days of operation. The competent (active) biomass fractions for these compounds were between 0.04% and 5.52% of the total biomass inferred from substrate-specific microbial enumerations. The measured competent biomass fractions for 4-chlorophenol and 3-nitrobenzoate degradation were significantly lower than the influent COD fractions of these compounds. Correspondent to the highest competent biomass fraction for benzoate degradation among the test SOCs, benzoate oxidation could be quantified with an extant respirometric technique, with the highest specific oxygen uptake rate (SOUR(benzoate), 0.026 g O2 h(-1) g(-1) XCOD) in the anoxic/aerobic SBR. These combined results suggest that operating SBRs with alternative anoxic/aerobic cycles might facilitate the formation of granular sludge with good settleability, and retain comparable removal of nitrogen and synthetic organic compounds. Hence, the practice of anoxic/aerobic cycling should be considered in wastewater treatment systems whenever possible.     

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

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

利用同步臭氧氧化实现SBR污泥减量的研究

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

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

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

Development of particle-based biofilms for degradation of xenobiotic organic compounds

The aim of the experiments performed in this work was to develop a biofilm airlift suspension (BAS) process for the degradation of a mixture of organic sulfonates contained in the infiltration water from a contaminated site. To achieve this goal, active biomass growing on the contaminating xenobiotic organics as the sole source of carbon was obtained by enriching a mixed microbial culture sampled from an activated sludge treatment plant. After kinetic characterisation, the enriched culture was inoculated in the BAS reactor, where it colonised carrier particles and formed stable and uniform biofilms. In spite of the slow growth and degradation kinetics (mu(max)=0.014 h(-1)), due to high biomass concentration (up to 12 g(VS)L(-1)) a high rate process was performed in the BAS reactor, achieving a degradation capacity of 8.7 kg(COD)m(-3)d(-1), with an overall degradation efficiency of 70% based on COD measurements.     

Ozonation kinetics of cork-processing water in a bubble column reactor

The oxidative degradation of organic pollutants present in cork-processing water at natural pH (6.45) was studied in a bubble column ozonation reactor. A steady reduction in both chemical oxygen demand (COD) and total organic carbon (TOC) was observed under the action of ozone alone and the feasibility of deep mineralisation (organic matter removal more than 90% in 120 min under the following experimental conditions: liquid volume 9L; superficial gas velocity 6.8x10(-3) m s(-1); ozone partial pressure 1.31 kPa; initial COD 328 mg L(-1); initial TOC 127 mg L(-1)) was demonstrated. The monitoring of pH, redox potential (ORP) and the mean oxidation number of carbon (MOC) was correlated with the oxidation and mineralisation of the organic species in the water. The ozonation of cork-processing water in the bubble column was analysed in terms of a mole balance coupled with ozonation kinetics modelled by the two-film theory of mass transfer and chemical reaction. Under the experimental conditions used, and in contrast with the literature, it was determined that the reaction follows a fast kinetic regime at the beginning of the oxidation process, shifting to the moderate and the slow kinetic regimes at later stages of the oxidation reaction. The dynamic change of the rate coefficient estimated by the model was correlated to changes in the water composition.     

Anaerobic treatment of real textile wastewater with a fluidized bed reactor

Anaerobic treatability of a real cotton textile wastewater was investigated in a fluidized bed reactor (FBR) with pumice as the support material. The immobilized biomass or attached volatile solids level on the support material was 0.073 g VSS/g support material at the end of the 128-d start-up period. During the operation period, real cotton textile wastewater was fed to the anaerobic FBR both unsupplemented (in Stages 1 and 2) and supplemented (with synthetic municipal wastewater in Stage 3 and glucose in Stages 4-6). The effect of operational conditions such as organic loading rate (OLR), hydraulic retention time (HRT), influent glucose concentration as the co-substrate, etc. was investigated to achieve the maximum color removal efficiency in the reactor. Results indicated that anaerobic treatment of textile wastewater studied was possible with the supplementation of an external carbon source in the form of glucose (about 2g/l). The corresponding maximum COD, BOD(5) and color removals were found to be around 82%, 94% and 59%, respectively, for HRT of around 24h and OLR of 3 kg COD/m(3)/d. Further increase in external carbon source added to real textile wastewater did not improve the color removal efficiency of the anaerobic FBR reactor.     

Elimination of beta-blockers in sewage treatment plants

beta-Blockers are used to treat high blood pressure as well as patients recovering from heart attacks. In several studies, they were detected in surface water, thus indicating incomplete degradability of these substances in sewage treatment plants (STPs). In this study, we determined the sorption coefficients (K(D)) and degradation rates of the four beta-blockers sotalol, atenolol, metoprolol and propranolol in sludge from an STP operating with municipal wastewater. The sorption coefficients (K(D), standard deviations in brackets) were determined as 0.04(+/-0.035), 0.04(+/-0.033), 0.00(+/-0.023) and 0.32(+/-0.058) Lg(-1)(COD), and the pseudo-first-order degradation rate constants were estimated to be 0.29(+/-0.02), 0.69(+/-0.05), 0.58(+/-0.05) and 0.39(+/-0.07) Ld(-1)g(-1)(COD) for sotalol, atenolol, metoprolol and propranolol, respectively. These values translate into a typical elimination in STPs (sludge concentrations of 4g(COD)L(-1) and a hydraulic retention time of 6h) of 25%, 37%, 44% and 50% for sotalol, propranolol, metoprolol and atenolol, respectively. These results are also confirmed by measurements in two municipal STPs for atenolol, sotalol and propranolol. The estimated eliminations are slightly too high for metoprolol.     

Effect of NaCl on thermophilic (55 degrees C) methanol degradation in sulfate reducing granular sludge reactors

The effect of NaCl on thermophilic (55 degrees C) methanol conversion in the presence of excess of sulfate (COD/SO(4)(2-)=0.5) was investigated in two 6.5L lab-scale upflow anaerobic sludge bed reactors inoculated with granular sludge previously not adapted to NaCl. Methanol was almost completely used for sulfate reduction in the absence of NaCl when operating at an organic loading rate of 5 g CODL(-1)day(-1) and a hydraulic retention time of 10h. The almost fully sulfidogenic sludge consisted of both granules and flocs developed after approximately 100 days in both reactors. Sulfate reducing bacteria (SRB) outcompeted methane producing archaea (MPA) for methanol, but acetate represented a side-product, accounting for maximal 25% of the total COD converted. Either MPA or SRB did not use acetate as substrate in activity tests. High NaCl concentrations (25 gL(-1)) completely inhibited methanol degradation, whereas low salt concentrations (2.5 g NaClL(-1)) provoked considerable changes in the metabolic fate of methanol. The MPA were most sensitive towards the NaCl shock (25 gL(-1)). In contrast, the addition of 2.5 gL(-1) of NaCl stimulated MPA and homoacetogenic bacteria.     

Treatment of anaerobically pre-treated domestic sewage by a rotating biological contactor.

The performance of a rotating biological contactor (RBC) for the post-treatment of the effluent of an up-flow anaerobic sludge blanket (UASB) was the subject of this study. Different hydraulic and organic loading rates have been investigated. The removal efficiencies of COD(total), COD(suspended), COD(colloidal) and COD(soluble) increased at a higher hydraulic retention time (HRT) and a lower influent organic loading rate. The results obtained indicated that a two-stage RBC reactor at an HRT of 10 h and an organic loading rate of 6.4g COD m(-2) d(-1) represents an effective post-treatment process. Most COD(suspended) and COD(colloidal) were removed in the first stage while nitrification proceeded in the second stage. The overall nitrification efficiency was 92% at an ammonia loading rate of 1.1 gm(-2) d(-1). Total E. coli removal at HRTs of 10, 5 and 2.5h were 99.5%, 99.0% and 89.0%. respectively. The major part of suspended E. coli ( >4.4 microm) was removed by sedimentation or by adsorption in the biofilm of the first stage of RBC (99.66%). However, E. coli in the colloidal fraction (<4.4 to >0.45 microm) was eliminated in the second stage of RBC (99.78%). A comparison of the performance of a one-stage versus two-stage RBC system, operated at the same total loading rate, revealed an improvement in the effluent quality of the two-stage effluent as compared to the one-stage effluent. The two stages RBC were used to examine the effect of hydraulic shock loads on reactor performance in terms of COD, nitrification and E. coli removal.     

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

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

Ozonation of naphthalene sulfonic acids in aqueous solutions: part II--relationships of their COD,TOC removal and the frontier orbital energies

This paper evaluated the COD, TOC removal and molecular frontier energies in the ozonation of naphthalene sulfonic acids (NSAs). It was found that both COD and TOC degradation of the 11 compounds followed the pseudo-first-order kinetic and the reaction rate constants with ozone varied widely. A linear relationship between logarithm of global COD degradation rate constant and the energy of the highest occupied molecular orbit, E(homo), was obtained for these NSAs with a regression coefficient of 0.88 and a slope of 0.4672 eV(-1). TOC degradation kinetics also reached similar results with a regression coefficient of 0.90 and a slope of 0.9336 eV(-1). The results of correlation analysis suggested that TOC and COD removal in ozonation of NSAs follow the frontier orbital theory and can be predicted by E(homo), which indicated that electrophilic effect was the main factor in the ozonation of NSAs. Therefore, it is possible to improve the biodegradability of dyestuff wastewater bearing mainly NSAs by ozonation at an accepted cost and evaluate the economy of ozonation process.