Ana Loncaric Bozic

Environmental aspects of photooxidative treatment of phenolic compounds

The study was aimed at evaluation of environmental aspects on photooxidative treatment of phenolic compounds by UV/H2O2 process. Hydroxy-, chloro-, nitro- and methyl-phenols substituted in ortho and para positions were used as model pollutants. The influence of pollutant chemical structure on variations of water quality during the photooxidative treatment was investigated. In that purpose, we monitored the changes of total organic carbon (TOC); chemical oxygen demand (COD); aromaticity, measured as absorbance at 280 (A280) and 254 nm (A254); biodegradability, estimated over ratio of biochemical and chemical oxygen demand (BOD5/COD); and toxicity, estimated on inhibition of Vibrio fischeri luminescence (TU). It was found that changes of monitored parameters are influenced by the type and position of substituent. Studied pollutants share sequence in degradation pathway and consequently some of the formed by-products are the same as well. However, their distribution and the formation of specific by-products with characteristic functional groups play significant role in observed variations of water quality, which was particularly reflected in biodegradability and toxicity. The cross-correlation between recorded sum-water parameters is assessed on the basis of calculated Spearman rank coefficients.

Photooxidation of benzene-structured compounds: influence of substituent type on degradation kinetic and sum water parameters.

The combined influence of substituent type and UV/H(2)O(2) process parameters on the degradation of four aromatic water pollutants was investigated using modified 3(3) full factorial design and response surface methodology. Degradation kinetics was described by the quadratic polynomial model. According to the applied ANOVA, besides pH and [H(2)O(2)], model terms related with the pollutant structure are found to be significant. Different optimal operating conditions and values of observed degradation rate constants were determined for each of the pollutants indicating that the type of substituent influences the overall process effectiveness over structurally defined degradation pathway. Biodegradability (BOD(5)/COD) and toxicity (TU) were evaluated prior to the treatment and at the reference time intervals t(1/2)(P), t(3/4)(P), t(1/4)(OC) and t(1/2)(OC) corresponding to the real time required to reduce the concentration of parent pollutant and organic content for 1/2, 3/4, 1/4 and 1/2 of initial amount. The observed differences are correlated to the structural differences of studied aromatics.

Solar-driven photocatalytic treatment of diclofenac using immobilized TiO2-based zeolite composites

The study is aimed at evaluating the potential of immobilized TiO2-based zeolite composite for solar-driven photocatalytic water treatment. In that purpose, TiO2-iron-exchanged zeolite (FeZ) composite was prepared using commercial Aeroxide TiO2 P25 and iron-exchanged zeolite of ZSM5 type, FeZ. The activity of TiO2-FeZ, immobilized on glass support, was evaluated under solar irradiation for removal of diclofenac (DCF) in water. TiO2-FeZ immobilized in a form of thin film was characterized for its morphology, structure, and composition using scanning electron microscopy/energy-dispersive x-ray spectroscopy (SEM/EDX). Diffuse reflectance spectroscopy (DRS) was used to determine potential changes in band gaps of prepared TiO2-FeZ in comparison to pure TiO2. The influence of pH, concentration of hydrogen peroxide, FeZ wt% within the composite, and photocatalyst dosage on DCF removal and conversion efficiency by solar/TiO2-FeZ/H2O2 process was investigated. TiO2-FeZ demonstrated higher photocatalytic activity than pure TiO2 under solar irradiation in acidic conditions and presence of H2O2.

Treatment of Chlorophenols by UV-Based Processes: Correlation of Oxidation By-Products, Wastewater Parameters, and Toxicity

The aim of the study was to evaluate the toxicity and biodegradability of para-chlorophenol (p-CP) model wastewater when treated by UV and UV/H2O2 processes. We investigated the correlations between the toxicity and the concentration of p-CP and its oxidation by-products, as well as other parameters—summarizing characteristics which potentially indicate hazardous water components, e.g., AOX (adsorbable organic halides), TOC (total organic carbon), and COD and BOD5 (chemical and biochemical oxygen demand). Biodegradability is estimated by the BOD5/COD ratio. The toxic effects were investigated on luminescent bacteria Vibrio fischeri, determining the EC50 value. The correlation between each data pair was estimated using a statistical approach calculating the Spearman rank coefficients. The biodegradability of the p-CP model wastewater was improved by the UV/H2O2 process; the BOD5/COD ratio increased from 0.37 to 0.73 after a 1-h treatment (F=1243  mJ cm-2). According to the calculated Spearman rank coeffici...

Prediction of biodegradability of aromatics in water using QSAR modeling

The study was aimed at developing models for predicting the biodegradability of aromatic water pollutants. For that purpose, 36 single-benzene ring compounds, with different type, number and position of substituents, were used. The biodegradability was estimated according to the ratio of the biochemical (BOD5) and chemical (COD) oxygen demand values determined for parent compounds ((BOD5/COD)0), as well as for their reaction mixtures in half-life achieved by UV-C/H2O2 process ((BOD5/COD)t1/2). The models correlating biodegradability and molecular structure characteristics of studied pollutants were derived using quantitative structure-activity relationship (QSAR) principles and tools. Upon derivation of the models and calibration on the training and subsequent testing on the test set, 3- and 5-variable models were selected as the most predictive for (BOD5/COD)0 and (BOD5/COD)t1/2, respectively, according to the values of statistical parameters R2 and Q2. Hence, 3-variable model predicting (BOD5/COD)0 possessed R2=0.863 and Q2=0.799 for training set, and R2=0.710 for test set, while 5-variable model predicting (BOD5/COD)1/2 possessed R2=0.886 and Q2=0.788 for training set, and R2=0.564 for test set. The selected models are interpretable and transparent, reflecting key structural features that influence targeted biodegradability and can be correlated with the degradation mechanisms of studied compounds by UV-C/H2O2.

Comparative analysis of UV-C/H2O2 and UV-A/TiO2 processes for the degradation of diclofenac in water

The study investigates the treatment of diclofenac (DCF), a pharmaceutical included in the first watch list of the European Water Framework Directive as a new potential priority substance in water. Since the conventional wastewater treatment technologies do not efficiently remove DCF, advanced treatment technologies capable of its complete removal or destruction of its biological activity, need to be evaluated and eventually employed. For that purpose, typical representatives of photooxidative and photocatalytic advanced oxidation processes were applied. The effectiveness of UV-C/H2O2 and UV-A/TiO2 were compared regarding DCF conversion and mineralization kinetics, water quality parameters for assessing biodegradability and toxicity. In spite of similar biodegradability profiles, the obtained results indicate different DCF degradation pathways, which are reflected in different profiles of toxicity towards Vibrio fischeri. The observed DCF conversion and mineralization kinetics revealed the benefits of UV-C/H2O2 process. However, lower toxicity favored the application of photocatalytic over photooxidative treatment for DCF removal.

Structural Influence on Photooxidative Degradation of Halogenated Phenols

The influence of structure on degradation of five halogenated phenols (XPs) by UV/H2O2 process was investigated. The combined influence of type or number of substituents and UV/H2O2 process parameters (pH and [H2O2]) on the degradation kinetics of 2-fluorophenol (2-FP), 2-chlorophenol (2-CP), 2-bromophenol (2-BP), 2,4-dichlorophenol (2,4-DCP), and 2,4,6-trichlorophenol (2,4,6-TCP) was studied using modified miscellaneous 33 full factorial design and response surface modeling (RSM). Studied XPs obey first-order degradation kinetics within the investigated range of process parameters. Determined degradation rate constants (kobs) were correlated with process and structural parameters by the quadratic polynomial models. Analysis of variance (ANOVA) demonstrated RSM models’ accuracy and showed that, in addition to pH and [H2O2], model terms related with the pollutant structure are highly influential. kobs of mono-XPs follow the decreasing order 2-FP, 2-CP, and 2-BP, while CPs follow the decreasing order 2-CP, 2,4-DCP, and 2,4,6-TCP. Biodegradability (biochemical oxygen demand (BOD)5/chemical oxygen demand (COD)) and toxicity (TU) were evaluated prior to the treatment and at the reference time intervals. The observed differences are correlated with the structural characteristics of studied XPs.

Application of Sensitivity and Flux Analyses for the Reduction of Model Predicting the Photooxidative Degradation of an Azo Dye in Aqueous Media

The prediction of the system behavior is of significant interest when evaluating appropriate technologies for wastewater treatment. The robust prediction could be achieved by empirical mathematical modeling techniques, but they do not include steps in degradation of organic pollutants. Mechanistic models (MM) include chemical/physical phenomena, but may also include numerous reactions resulting with the complicated kinetic expressions with large number of parameters. This modeling approach can be challenging for complex system such as advanced oxidation processes. With the goal to reduce the number of reactions involved in developed MM, keeping the high prediction power, sensitivity, and flux analyses was employed. The results showed that MM describing the degradation of organic dye in water matrix by photooxidation processes can be significantly simplified, by reducing the number of reactions included without affecting the predictive power. The calculated root mean square deviation values between data predicted by MM and reduced MMR differ insignificantly (≤1.4 %).

Influence of process parameters on the effectiveness of photooxidative treatment of pharmaceuticals

ABSTRACT In this study, UV-C/H2O2 and UV-C/ processes as photooxidative Advanced oxidation processes were applied for the treatment of seven pharmaceuticals, either already included in the Directive 2013/39/EU “watch list” (17α- ethynylestradiol, 17β-estradiol) or with potential to be added in the near future due to environmental properties and increasing consumption (azithromycin, carbamazepine, dexamethasone, erythromycin and oxytetracycline). The influence of process parameters (pH, oxidant concentration and type) on the pharmaceuticals degradation was studied through employed response surface modelling approach. It was established that degradation obeys first-order kinetic regime regardless structural differences and over entire range of studied process parameters. The results revealed that the effectiveness of UV-C/H2O2 process is highly dependent on both initial pH and oxidant concentration. It was found that UV-C/ process, exhibiting several times faster degradation of studied pharmaceuticals, is less sensitive to pH changes providing practical benefit to its utilization. The influence of water matrix on degradation kinetics of studied pharmaceuticals was studied through natural organic matter effects on single component and mixture systems.

Reactivation and reuse of TiO2-SnS2 composite catalyst for solar-driven water treatment

One of the most important features of photocatalytic materials intended to be used for water treatment is their long-term stability. The study is focused on the application of thermal and chemical treatments for the reactivation of TiO2-SnS2 composite photocatalyst, prepared by hydrothermal synthesis and immobilized on the glass support using titania/silica binder. Such a catalytic system was applied in solar-driven treatment, solar/TiO2-SnS2/H2O2, for the purification of water contaminated with diclofenac (DCF). The effectiveness of studied reactivation methods for retaining TiO2-SnS2 activity in consecutive cycles was evaluated on basis of DCF removal and conversion, and TOC removal and mineralization of organic content. Besides these water quality parameters, biodegradability changes in DCF aqueous solution treated by solar/TiO2-SnS2/H2O2 process using simply reused (air-dried) and thermally and chemically reactivated composite photocatalyst through six consecutive cycles were monitored. It was established that both thermal and chemical reactivation retain TiO2-SnS2 activity in the second cycle of its reuse. However, both treatments caused the alteration in the TiO2-SnS2 morphology due to the partial transformation of visible-active SnS2 into non-active SnO2. Such alteration, repeated through consecutive reactivation and reuse, was reflected through gradual activity loss of TiO2-SnS2 composite in applied solar-driven water treatment.