Comparison of Photocatalytic and Photosensitized Oxidation of Paraben Aqueous Solutions Under Sunlight.

It is well-established that aquatic wildlife is exposed to natural and synthetic endocrine disrupting compounds which are able to interfere with the hormonal system. Although advanced oxidation processes (AOPs) have shown to be effective, their application is limited by a relatively high operational cost. In order to reduce the cost of energy consumed in the AOPs, widely available solar energy instead of UV light may be applied either as photocatalytic oxidation or as photosensitized oxidation. The main goal of the present study was to investigate the sunlight photodegradation of paraben mixture. Two processes, namely the photocatalytic oxidation with modified TiO2 nanoparticles and photosensitized oxidation with photosensitive chitosan beads, were applied. The oxidants were identified as singlet oxygen and hydroxyl radicals for photosensitized and photocatalytic oxidation, respectively. The toxicity, as well as ability to water disinfection of both processes under natural sunlight, has been investigated. Application of sunlight for the processes led to degradation of parabens. The efficiency of both processes was comparable. Despite the fact that singlet oxygen is weaker oxidant than hydroxyl radicals, the photosensitized oxidation seems to be more promising for wastewater purification, due to the possibility of chitosan bead reuse and more effective water disinfection. Graphical Abstractᅟ.

Decomposition of xenobiotics during visible light irradiation in the presence of immobilised photosensitisers: kinetics study.

The objective of this work was to study the photosensitised oxidation of the xenobiotics benzylparaben (BeP) and 2,4dichlorophenol (2,4DCP) in aqueous solutions using photosensitisers immobilised into chitosan carrier particles and visible light radiation. Zn(II) phthalocyanine tetrasulfonate tetrasodium salt and Al(III) phthalocyanine chloride tetrasulfonic acid were used as photosensitisers. The major role of the singlet oxygen during photodegradation was proven by using scavengers of reactive oxygen species. The influence of initial xenobiotic concentration and temperature on degradation rate was examined. The investigations were focused on kinetics (Langmuir-Hinshelwood model) as well as activation energy determination. Moreover, the adsorption isotherms of BeP and 2,4DCP into chitosan carrier were determined using the Brunauer-Emmett-Teller model.

Singlet molecular oxygen application for 2-chlorophenol removal.

A special kind of photocatalysis-a photosensitized oxidation involving singlet molecular oxygen ((1)O(2)) was applied to decomposition of 2-chlorophenol (2-CP) in water solution. The photoprocess was carried out in a homo- and heterogeneous system using rose bengal (RB) as a sensitizer. In the homogeneous solution the influence of initial 2-CP concentration and pH on reaction rate was observed. Based on the kinetic model, the rate constants of (1)O(2) quenching and reaction with 2-CP and the rate constant of excited sensitizer quenching by 2-CP were determined. In the heterogeneous system, silane gel was a carrier for the immobilized sensitizer. In order to estimate kinetic parameters, an attempt was made to describe the process using Langmuir-Hinshelwood (L-H) type mechanism. The Langmuir equilibrium constants for oxygen and 2-CP adsorbed on the gel surface were also estimated.

Microbial removal of ionic mercury in a three-phase fluidized bed reactor.

The reductive biotransformation of mercuric ions to elemental mercury was studied by applying a model system with a genetically engineered Pseudomonas putida strain in a lab scale three-phase fluidized bed (TPFB). The aim was to demonstrate the suitability of the TPFB to demercurize effluent streams containing up to 10 mg Hg2+ dm(-3). The TPFB is used, first, to carry out the biotransformation on the alginate immobilized biocatalyst and, second, to remove the produced Hg0 by volatilization into the gas phase followed by its recovery through fast oxidative absorption. Targeted experiments with the immobilized biocatalyst were designed and carried out to determine mercury adsorption data on the biomass and all relevant mass transport rates at conditions prevailing in the TPFB. The evaluation of the performance data in the TPFB revealed almost complete reaction control and hence negligibility of mass transfer resistances. This simplifies the scale-up of larger TPFB reactors for mercury removal as it can be based on the known kinetics alone. The measured biotransformation capacities in the TPFB are similar to those reported for the fixed bed technology which has already proven its applicability at an industrial scale in long time runs. However, the TPFB offers some advantages over the fixed bed and could therefore possibly be a favorable, reliable, and less costly alternative to the existing technology.

Equilibrium and dynamic investigations of organic acids adsorption onto ion-exchange resins.

The aim of the study was to determine properties of selected ion-exchange resins for citric and lactic acids recovery, to define sorption isotherms for these acids at different temperatures (in the range of 20-60 degrees C) and to determine diffusion coefficients inside sorbent particles. A mathematical model of the ion-exchange process in the chromatographic column and its experimental verification is also presented. During investigations 18 types of ion-exchange resins were tested. It was found that weakly basic resins were more suitable for the recovery process than strongly basic ones. The best resin for the separation of citric acid was Amberlite IRA-67 and for lactic acid Amberlite IRA-92. As a result of transient-state sorption experiments diffusion coefficients of the citric acid inside the sorbent particle at different temperatures were obtained. It was found that D(p) increased with the temperature by two times in the range of 20-60 degrees C, and its value at 60 degrees C was 7.2 x 10(-10) m(2)/s. The proposed mathematical model was applied to identify bed operation parameters in the column for the needs of the simulated moving bed chromatography method.

Ozonation of Reactive Blue 81 in the bubble column.

The decolourisation process of the Reactive Blue 81 was carried out in a laboratory bubble column reactor with inner diameter 110 mm and working height 550 mm, equipped with a porous glass ozone diffuser (diameter 50 mm). A model of ozone absorption with the chemical reaction in the liquid phase was employed. It was found that the decolourisation proceeds in the fast pseudo first-order regime. The average value of the enhancement factor was calculated from the experimental results and compared with those calculated according to the theory of mass transfer with a second-order chemical reaction. In order to determine the intrinsic kinetics of ozonation, a stopped-flow technique was employed. The rate constant of the dyestuff reaction with ozone was determined as equal to 4.5 x 10(7) mol/(dm3.s).

Degradation of household biowaste in reactors.

Household derived biowaste was degraded by biological methods. The system involves the combined method of low-solids (up to 10% w/v of total solids (TS)) anaerobic digestion and aerobic degradation for the recovery of energy (biogas) and the production of fine humus-like material which can be used as a soil amender or a substrate for further thermal treatment (pyrolysis, gasification). The performance of batch and continuous processes carried out in bioreactors (stirred tank reactor, air-lift) of working volume 6 and 18 dm(3), at different temperatures (25-42 degrees C) was monitored by reduction of TS, volatile solids, chemical oxygen demand, total organic carbon, C/N in time. The application of continuous process with recirculation (33%) caused that for residence time of 8-16 h the obtained degree of organic load reduction was similar to that obtained after 72-96 h of the batch process. The experimental data of batch aerobic degradation was also subjected to kinetic analysis. The sequence of the two processes: aerobic and anaerobic or anaerobic and aerobic showed that the degree of organic load reduction was similar in both cases, while the amount of produced biogas was four times higher when the first stage was anaerobic. The final product after dewatering was subjected to pyrolysis and gasification. The gases obtained were characterised by a high heat of combustion of about 11-15 MJ Nm(-3).

Biodegradation, decolourisation and detoxification of textile wastewater enhanced by advanced oxidation processes.

Recently, an increasing application of so called advanced oxidation processes (AOPs) to industrial wastewater has been observed. In particular, an integrated approach of biological and chemical treatment of wastewater is advantageous conceptually. The subject of our study was synthetic wastewater, simulating effluents from knitting industry. The wastewater contained components that are very often used in Polish textile industry: an anionic detergent Awiwaz KG conc., a softening agent Tetrapol CLB and an anthraquinone dyestuff-Acid Blue 40, CI 2125. The toxicity of the detergents and the dye was determined in terms of effective concentration EC50 using mixed cultures of activated sludge as well as pure culture of luminescent bacteria Vibrio fischerii NRRLB-11177. The dye did not undergo biodegradation without AOPs pretreatment, therefore a degree of its removal (decolourisation) by the AOPs has been determined and its bio-sorption properties on the flocks of activated sludge have been studied. The dye adsorption onto flocks of activated sludge was described by Henry's isotherm. Our investigations focussed on the influence of various oxidants like O3, H2O2 and UV light on biodegradation of single components aqueous solution as well as of the whole textile wastewater. The results of kinetic measurements of the biodegradation (by means of acclimated activated sludge) was described by Monod type of kinetic equation. The experimental evidence of the positive effect of chemical oxidation pretreatment on the biodegradation of recalcitrant compounds was quantified by estimation of the kinetic parameters of the Monod equation. Due to the AOPs pretreatment a decrease of the Monod constant and an increase of maximal specific growth rate was observed. The activity of degradative enzymes of activated sludge was assayed by the methods of 2-[4-iodophenyl]-3-[4-nitrophenyl]-5-phenyltetrazolium chloride test.

Thermal processing of sewage sludge by drying, pyrolysis, gasification and combustion.

Thermal processing of sewage sludge including drying, pyrolysis and gasification or combustion may be an alternative to other ways of utilising it. In this paper thermogravimetric analysis (TGA) was employed in the investigation of thermal decomposition of sewage sludge. The kinetic parameters of drying, pyrolysis and gasification or combustion of sewage sludge have been determined in an inert-gas (argon) and additionally some series of the sludge decomposition experiments have been carried out in air, in order to compare pyrolysis and combustion. The pyrolysis char has been gasified with carbon dioxide. A typical approach to the kinetics of thermal decomposition of a solid waste is to divide the volatile evolution into a few fractions (lumps), each of which is represented by a single first-order reaction. If these lumps are assumed to be non-interacting and evolved by independent parallel reactions the first-order kinetic parameters such as activation energy Ei and pre-exponential factor Ai can be determined from mathematical evaluation of TG or DTG curves. The object of our investigations was a municipal sludge from the two wastewater treatment plants (WTP) in Poland. The experiments have been carried out in the thermobalance Mettler-Toledo type TGA/SDTA851 LF, in the temperature range 30-1,000 degrees C. Five different values of heating rate have been applied beta = 2, 5, 10, 15 and 20 K/min. The values of Ei and Ai have been determined for all recognised lumps of gaseous products. The method employed has also revealed its usefulness for the determination of kinetic parameters for municipal sludge, that possess an undefined content. An alternative route to combustion of sewage sludge is its gasification, which significantly increases the gaseous product (pyrolytic gas + syngas). Besides pyrolysis kinetics, gasification or combustion process kinetics have also been determined.