Ozonation of swine manure wastes to control odors and reduce the concentrations of pathogens and toxic fermentation metabolites

The use of ozone for the remediation of nuisance odorous chemicals in liquid swine manure slurry was investigated. Gaseous ozone was bubbled directly into stored swine manure slurry in a continuously stirred batch reactor. One‐liter samples of swine slurry were ozonated to achieve ozone dosages of 1.0, 2.0 and 3.0 g ozone/liter of waste. Olfactometric determinations demonstrated a significant reduction in odors in ozonated samples as compared to raw and oxygenated samples. Volatile fatty acids, nitrate, phosphate and ammonia concentrations were unchanged by ozonation. The biochemical oxygen demand (BOD) and the chemical oxygen demand (COD) were essentially unaffected by ozonation. The concentrations of odorous phenolic microbial metabolites (e.g., phenol, p‐cresol and p‐ethylphenol) and odorous indolic microbial metabolites (e.g., 3‐methylindole and indole) were reduced to non‐detectable levels by ozonation. Hydrogen sulfide concentrations were reduced slightly by the process, with a concurrent increase in the sulfate concentration. E. coli counts were reduced by a factor of three log units and total coliforms showed a one log decrease in concentration after treatment with ozone at 1.0 g/L.

The results of this study demonstrate clearly that at the pH values studied (ca. 7), ozonation is effective for the elimination of the malodors associated with stored swine slurry and for killing potentially pathogenic bacteria, without increasing the concentrations of major pollutants of current concern, (i.e., nitrate and phosphate) and without oxidizing ammonia, which is a major plant nutrient.     

Formation of oxygen complexes by ozonation of carbonaceous materials prepared from cherry stones: I. Thermal effects

In this study, the feasible use of ozone to form oxygen complexes in chars prepared from cherry stones (CS) is investigated. CS were charred at 450, 600 or 900°C for 2 h in nitrogen. Char samples were ozonated over the 25-250°C temperature range for 1 h. Elemental chemical analysis was effected for a few selected samples. The oxygen complexes were successfully analyzed by Fourier infrared spectroscopy (FT-IR) and by titration methods. Thermal decomposition of ozone in the gas stream was also studied and the mechanism of the ozonation process dealt with. The ozonation treatment of CS chars was found to yield products with a relatively high concentration of a number of oxygen complexes. These include phenolic hydroxyl, quinonic, carboxylic acid, and ether structures. The content of lactonic structures was very low in the ozonated samples. The type and quantity of oxygen complexes depended on the ozonation and charring temperatures. The formation of oxygen complexes was favored when the charring of CS was effected at 450°C and when the ozonation of the char prepared at 600°C was performed at 100°C. The ozone content in the gas stream was very sensitive to the temperature increase in the reactor. Several reaction routes have been proposed for the transformation of ether, aromatic, and olefinic structures present in CS chars into oxygen complexes.     

Effects Of Ozone On Kraft Process Pulp Mill Effluent

Effluent from a kraft process pulp mill was studied in a batch reactor for ozone doses between 50 and 200 mg O₃/L to identify the relative suitability of ozone application locations in the treatment process and see the improvements in biotreatability of wastewaters from a kraft process pulp mill. Laboratory acclimatized seed were used for BOD tests for ozonated and unozonated samples. The inhibitory effects were minimized by using optimum dilutions. The studies were divided into three major sections: characterization of mill effluent; ozone system calibration, and reactor design; and ozonation of mill effluent. Seed for Biochemical Oxygen Demand tests were acclimatized in batch units for primary, bleach and secondary effluents separately. The inhibitory effects which were noted with unacclimatized seed, were reduced by using laboratory acclimatized seed and optimum dilution which were determined during the characterization phase.

The batch reactor designed for the studies consisted of a cylindrical section for holding effluent, and a top spherical section for ozone/oxygen mixture. The reactor proved to be effective for controlling ozone dose. The variation in the applied ozone dose was less than 5 mg/L.

Bleach and primary effluents were treated with 50 and 100 mg/L ozone doses. Duplicate experiments were conducted for these effluents. Secondary effluent was studied for 50,100,150 and 200 mg/L ozone doses. Six replicate experiments were conducted for 50 and 100 mg/L ozone doses, whereas two experiments were carried out for 150 mg/L and one experiment for 200 mg/L ozone dose.

The results were analyzed using 't' test for paired experiments and ANOVA table for statistical confirmation. Residuals were plotted to check the assumptions of constant variance and normal distribution. The results indicated that 50 and 100 mg O₃/L effectively removed color from bleach effluent and primary effluent, but did not significantly change the BOD. Ozone was found to be effective for secondary effluent, as BOD₅ was increased by 65% for 50 and 100% for 100 mg O₃/L doses. The corresponding reduction in color was 62% and 82%, respectively. K_e and L_o values for the BOD equation were calculated by using the non-linear least square method for the BOD equation, giving joint confidence regions for the calculated parameters. It was concluded that ozone is most effective for the removal of color and the increase of BOD in secondary effluent.     

Ozonation of Some Aromatic Compounds in Aqueous Solution: Styrene,Benzaldehyde, Naphthalene,Diethylphthalate, Ethyl and Chloro Benzenes

This study presents the ozonation of some of the aromatic compounds frequently found in French surface waters and which have not been the object of fundamental studies in an aqueous medium. As far as the reactivity is concerned, we have determined the values of the ozone consumed per initial aromatic consumed (molar ratio, ozone demand), in a semi batch bubble column at slightly acidic pH. As for the ozonation products, the application of specific experimental procedures in high concentration aqueous solution after the use of derivatization reactions, allowed us to isolate (PLC, GC) and identify (GC/HS ; MS, NMR) some degradation products in the cases of benzaldehyde and naphthalene. The following of the development, in dilute aqueous solution of some ozonation products (HPLC, GC), is presented in the cases of styrene, benzaldehyde, naphthalene and diethylphthalate. On the basis of the results obtained, the mechanisms of initial steps of ozonation are examined in the case of styrene, of benzaldehyde and of naphthalene. Lastly, with regards to chlorobenzenes and ethylbenzenes, it was not possible to isolate the ozonation products The stripping by ozonated gas of theses compounds became more significant evenof overwhelmingly greatimportance. The results obtained are discussed at the light of the previous results with ozonation of polar aromatic compounds.     

Formation of oxygen structures by ozonation of carbonaceous materials prepared from cherry stones: II. Kinetic study

In this second part, the kinetics of the ozonation process of a char prepared from cherry stones (CS) is investigated. The char was obtained by heat treatment of CS at 600°C for 2 h in nitrogen. The effects of reaction time, partial pressure of ozone, and mass transport phenomena on the formation of oxygen complexes are studied. The surface chemistry of the samples was examined by FT-IR spectroscopy and the elemental chemical analysis was also determined for some samples. Results showed that the ozonation of the char led to oxygen chemisorption and to carbon gasification. The amount of oxygen complexes formed in the chemisorption stage (i.e., OH groups, CO structures, and ether structures) was found to be very sensitive to the increase in the ozonation time. The type of oxygen complexes was also time dependent. Ozonated products with relatively high concentrations of CO groups and ether structures were prepared by applying high ozone doses, whereas the formation of OH groups was favored at low ozone contents. The particle size did not influence the surface chemistry of the ozonated products. Only when the gas flow rate was lower than 40 l h⁻¹, restrictions to ozone mass transport developed. For kinetics of the char ozonation process, a mechanism based on the Langmuir-Hinselwood adsorption-desorption model was proposed, and the intrinsic reaction rates were calculated as a function of ozonation temperature. The activation energy for the ozonation stage of the char was equal to 41.6 kJ mol⁻¹.     

Hydrophilicity Enhancement of High‐Density Polyethylene Film by Ozonation

High‐density polyethylene (HDPE) films were ozonated in the gas phase and in distilled water, respectively, to improve their surface hydrophilicity. The efficiency of ozonation conducted in the gaseous and aqueous phases was compared. The results indicated that the aqueous ozonation was more effective than its gaseous counterpart in terms of peroxide generation. The results also showed that the concentration of peroxides generated on the film surfaces increased with the applied ozone dose and ozonation time in both phases. It was found that the peroxides generated by aqueous ozonation were accessible to monomers for graft polymerization. The hydrophilicity of the HDPE films was significantly improved by graft polymerization of acrylamide (AAm) initiated by the peroxides. The contact angle reduction from 74.9° to 38.6° indicated the successful graft polymerization. The successful graft polymerization of AAm was further confirmed by the formation of new peaks corresponding to amide groups in FTIR spectra and by scanning electron microscope images.     

Post-Treatment of Composting Leachate by Ozonation

The post-treatment of composting leachate via an ozonation process in laboratory scale was studied in batch mode. According to the experiments, the COD removal was 47% after 30 min of ozonation via 0.4 g/h ozone (equivalent to 2.8 mg O₃/mg COD removed) at pH 9. In this circumstance, the removal of color and turbidity was also 86% and 89%, respectively. Increasing the ozone mass flow rate higher than 0.4 g/h had no considerable effect on the process variables. However, increasing the reaction time had a significant effect on both the removal of color and on COD of the leachate. Experimental data indicated that complete removal of color and 51% removal of COD were achieved after about 40 min of ozonation via 0.4 g/h ozone (equivalent to 3.3 mg O₃/mg COD removed). The ozone consumption rate increased as the reaction progressed and reached 4.1 mg O₃/mg COD removed after 60 min.     

Using Fractionated Natural Organic Matter to Quantitate Organic Byproducts of Ozonation

An improved procedure was used to isolate and fractionate natural organic matter (NOM) in water for subsequent ozonation and disinfection by-product (DBP) and color removal quantisation. Isolated NOM fractions from two different sources, accounting for approximately 50 to 60% of the dissolved organic material and 60 to 75% of the color, were characterized and then ozonated under conditions approximating those encontered during drinking water treatment. The natural waters also were ozonated. Organic DBPs of either health concern or which may contribute to biological instability of finished water were investigated, including aldehydes, oxoacids and low molecular weight carboxylic acids. pH and ozone dosage were the parameters having the greatest effect on DBP formation. On the basis of UV absorbance measurements, the fulvic acid fractions studied taken together accurately represented the natural water and may be the primary sources of precursor material for aldehydes and oxoacid DBPs. However, as yet unidentified NOM fractions contribute significantly to carboxylic acid formation upon ozonation.     

Heterogeneous Catalytic Ozonation of Aqueous Reactive Dye

The aqueous solution of a model reactive dye, C.I. Reactive Blue 5, was ozonated in the presence of a heterogeneous catalyst, CuS. It was found that CuS was very effective for catalyzing the decolorization so that both treatment time and ozone consumption were significantly reduced. For 1 g/L of the reactive dye, the stoichiometric ratios of ozone to dye in catalyzed and noncatalyzed ozonations were 2.7 and 10.6 (moles of ozone consumed)/(moles of dye oxidized), respectively, and the optimum catalyst load was 0.4 g/L. Although the noncatalytic ozonation was pseudo-first-order and the apparent pseudo-first-order rate constant declined with initial dye concentration logarithmically, in contrast, the experimental results showed that the catalytic ozonation was pseudo-second-order and the apparent pseudo-second-order rate constant decreased with initial dye concentration semilogarithmically. It was observed that the efficacy of ozone decolorization was higher at low pH and a scavenger test revealed that the amount of free radicals were negligible during ozonation. The experimental data further indicated that increase in temperature would increase the rate of the catalytic ozonation, however, the increment in the rate was not significant beyond 20°C.     

Effect of the ozonation process on the dyeability of mohair fibres

This work has focused on the use of ozonation in order to improve the dyeability of mohair fibres. The study was carried out using a known concentration of ozone and involved process parameters such as wet pick‐up, level of pH and treatment time. The effect of fibre ozonation was assessed in terms of colour, and test samples were also evaluated using scanning electron microscopy and Fourier transform–infrared spectroscopy. The optimum conditions of the ozonation process were determined as 60% wet pick‐up, pH 7 and 30 min. According to the experimental results, it can be concluded that ozonated mohair fibres can be dyed both at 90 and 80 °C with all dye classes without causing any decrease in colour yield. Dyeing kinetics and thermodynamics were also studied and it was demonstrated that the rate constant and the standard affinity of the ozonated sample increased.     

Simulation Of Ozone Transfer In Water. Comparison With A Pilot Unit

A computer simulation of a bubble column is established to determine the residual ozone concentration in the air and the dissolved ozone residual in the water. This study is aimed to improve the control of ozonation systems, both technically and economically.

The program is based on mass balances along the contact column, which take into account the ozone consumption due to both the self-decomposition and the reactions with organic compounds contained in the water. The experimental measurements allow quantification of the ozone concentration in the air at the inlet and outlet of the pilot unit, as well as the dissolved ozone concentration at different heights along the column. A relation between the transfer coefficient, k_La, and the superficial velocity of the ozonated air is established. It is specific to the diffusion characteristics of the pilot unit. The k_La then is reintroduced in the program.

The calculated and the measured values are shown to be similar regarding the transfer yields, the dissolved ozone concentrations at the pilot unit outlet and the profiles of dissolved ozone concentrations along the contact column. Using the program, the influence of the most important parameters of ozonation on the transfer (treatment rates, initial ozone concentration in the air, pH and organic content of the water, k_La values) have been simulated.     

The Determination of Carbonyl Compounds in Ozonated Water by the PFBOA Method

PFBOA, O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine, is excellent as a derivatizing agent in the GC determination of carbonyl compounds in ozonated water samples. Surface and waste waters have been ozonated. The carbonyl ozonation by-products were identified as PFBOA derivatives by gas chromatography-mass spectrometry. The main by-products of ozonation identified were formaldehyde, glyoxal, methylglyoxal, and 13 other compounds. The characteristics of the first three compounds with respect to production and decomposition during ozonation are discussed.     

Hydrolysis of freshly prepared wheat starch fractions and commercial wheat starch using α-amylase

The enzymic hydrolysis of commercial wheat starch and freshly prepared wheat starch fractions was studied in batch and flow systems. Fresh starch was prepared by wet separation of wheat flour into starch milk and gluten, followed by processing the starch milk using a serially connected hydrocyclone system to produce underflow and overflow streams. The underflow stream consisted mainly of the larger (> 30 w m) granules, while the overflow stream contained only the smaller (< 10 w m) granules. In batch system, the hydrolysis behavior of wheat starch fractions was investigated under the action of Sigma f -amylase ( Bacillus licheniformis ), either as soon as they were prepared or after spray drying. The two fractions of fresh wheat starch showed different hydrolysis behavior, the difference getting larger as the separation improves. Underflow streams were found to be much more susceptible to hydrolysis than overflow streams, regardless of whether the hydrolysis was carried out right away or on dried samples, and also regardless of whether rinsing was applied. In flow system, dried underflow stream and commercialwheat starch were hydrolyzed using Orbamil-T ( Bacillus licheniformis ), Orbamil-BHT ( Bacillus stearothermophilus ), and Sigma f -amylase ( Bacillus licheniformis ). Hydrolysis of fresh starch was found to be significantly faster than commercial wheat starch. Commercial f -amylase Orbamil-T was found to be almost as effective as the purified Sigma f -amylase.     

Ozonated Mineral Oil: Preparation,Characterization and Evaluation of the Microbicidal Activity

The ozonation of vegetable oils has been studied, since the produced ointments have antibacterial and fungicidal activities. However, the ozonation of mineral oils has not been reported in the literature yet, opening an interesting field for examination. In this work, we have shown the ozonation of a commercial mineral oil (Nujol). The main goal was to produce oils containing free ozone, so that this gas could act as antimicrobial agent. It was found that in Nujol, ozone remains for at least 40 days and in the sample ozonized for 15 h its concentration was 7.5 mg mL^?1. Neat Nujol showed no antimicrobial activity against the tested microorganisms, however, when ozonated it showed antimicrobial activity against Enterococcus faecalis, Staphylococcus aureus and Escherichia coli.     

Quinoxaline Ozonation in Aqueous Solution

The oxidation of quinoxaline by ozone in aqueous solution is investigated. The chemical and kinetic evolution of the oxidation process at varying pH are followed by means of semi-batch and batch ozonation experiments. Results indicate that quinoxaline ozonation can develop according to both radical and ionic mechanisms whose relative occurrence can be varied by means of addition to the reacting system of radical scavengers or ozone decomposition promoters. It is shown that each mechanism involves an initial attack of ozone to both the homocyclic and heterocyclic rings of quinoxaline. Pyrazinedicarboxylic acid is formed as a stable final product in ionic ozonation, whereas it appears as an intermediate still reactive towards ozone in radical ozonation. Despite this, the radical ozonation of quinoxaline appears to be more selective than ionic zonation with respect to production of pyrazinedicarboxylic acid. Reaction schemes are proposed to account for the observed kinetic behaviors and product formations.

Oxidation experiments have also been extended to pyrazine, and its sensitivity to only radical ozonation is shown.     

Effect of Ozonation on Biodegradability Characteristics of Surplus Activated Sludge

The study investigates the effect of sludge ozonation on solid matter species, disintegration properties, sludge components, and solubilization characteristics under different operating conditions. Ozonation of surplus activated sludge samples taken from the secondary settling tank of a domestic wastewater treatment plant indicates that soluble nitrogen, phosphorus and COD concentrations proliferate as a consequence of extending the ozone feeding time. A steady increase both in soluble nitrogen concentration and ratio of organic phosphorus to soluble phosphorus is observed through ozonation where specific ozone doses range between 4 and 11 mg O₃/g SS. Combined treatment of chemical oxidation and aerobic biodegradation to surplus activated sludge is also applied to improve the biodegradability of organic matter by partial chemical oxidative pretreatment with as little specific ozone consumption as possible. The partial oxidation by integrated ozonation is operated as a pre-oxidation step for the subsequent biological degradation, due to the fact that the competition with biological degradation in removing biodegradable organic compounds is avoided and most probably a more biodegradable sludge composition is obtained by means of ozonation. Combined treatment of chemical oxidation and aerobic biodegradation conducted to scrutinize the synergic effect of the coupled treatment system reveals that TS and COD removal efficiencies of ozonated sludge samples cannot be improved beyond the third aerobic biodegradation step.     

Oxidation of Organic Pollutants of Water to Mineralization by Catalytic Ozonation

The oxidation of various organic compounds in aqueous solution was studied using catalytic ozonation (TOCCATA process) and conventional ozonation. The aim of the work is to assess catalytic ozonation efficiency for the mineralization of various organic compounds in order to envisage its application on real effluents. The selected organic compounds (about 30) are commonly found in industrial wastewaters. Comparative experiments were performed in batch mode at laboratory scale. Investigations were focused on ozone consumption rate, variations of total organic carbon, oxidation by-products and oxidation rate. Catalytic and conventional ozonation treatments were compared considering kinetic data, mineralization extent, and effect of organic functionalities. Catalytic ozonation system according to the TOCCATA process was able to convert organic compounds which were totally inert to ozone treatment and permitted considerably enhanced reaction rates when compounds were reactive to ozonation.     

Practical Guidelines For Safe Operation Of Cooling Tower Water Ozonation Systems

Guidelines for the successful use of ozone as a stand-alone cooling tower water treatment method are discussed. Included are recommendations for system sizing, proper ozone residuals, mixing and distribution of the ozonated water, and potential problems and solutions. These include excessive or insufficient cycles of concentration, chemical contamination, low flow rates, high heat exchanger temperatures, and extended system turnover times. Also discussed are recommended maximum system downtimes, preferred types of towers and heat exchangers to treat with ozone, use of filtration systems, and elastomer compatibility with ozone. System monitoring and maintenance procedures are discussed along with ozonation safety considerations. With this information, two recently reported ozonation system failures are analyzed and the causes of failure are discussed.     

Post-Treatment of Pulp and Paper Industry Wastewater by Advanced Oxidation Processes

The aim of this study was to investigate the effectiveness of chemical oxidation by applying ozonation, combination of ozone and hydrogen peroxide and Fenton's processes for decolorization and residual chemical oxygen demand (COD) removal of biologically pretreated pulp and paper industry effluents. The batch tests were performed to determine the optimum operating conditions including pH, O₃, H₂O_2, and Fe²⁺ dosages. H₂O₂ addition reduced the reaction times for the same ozone dosages; however combinations of ozone/hydrogen peroxide were only faintly more effective than ozone alone for COD and color removals. In the Fenton‘s oxidation studies, the removal efficiencies of COD, color and ultraviolet absorbance at 254 nm (UV₂₅₄) for biologically treated pulp and paper industry effluents were found to be about 83, 95, and 89%, respectively. Experimental studies indicated that Fenton oxidation was a more effective process for the reduction of COD, color, and UV₂₅₄when compared to ozonation and ozone/hydrogen peroxide combination. Fenton oxidation was found to have less operating cost for color removal from wastewater per cubic meter than the cost for ozone and ozone/hydrogen peroxide applications.