Mariángel Martín

p-Nitrophenol (PNP) is a compound with numerous applications in the chemical industry. PNP is mainly used in the manufacturing industry of pharmaceutical products, pesticides and leather-related products. PNP is highly toxic for humans, animals and the environment. Repeated exposure to PNP may cause injury to blood cells, damage to the central nervous system and mutagenic effects. Selecting the appropriate process to treat wastewaters containing recalcitrant compounds, such as PNP, is greatly dependent on the nature of the compound itself, its concentration and its loading rate. In this thesis, a comparative study on the treatment of high-strength wastewaters containing PNP is intended by taking different approaches according to the wastewater characteristics. Firstly, biological treatment in an aerobic Sequencing Batch Reactor (SBR) was studied. The start up of the reactor was performed using a non-acclimated biomass, coming from a municipal wastewater treatment plant as inoculum and a synthetic wastewater containing a mixture of PNP and glucose-sucrose as carbon source. A specific operational strategy was applied with the aim of developing a K-strategist PNP-degrading activated sludge. Total PNP removal was achieved in the whole operating period. Kinetic characterization of the PNP-degrading population was carried out using respirometry assays. The kinetic values obtained confirmed that the biomass was of K-strategist type, thus demonstrating the success of the operational strategy. The Ki value obtained in this work was higher than others reported in the literature, meaning that the sludge was more adapted to PNP inhibition. Afterwards, bioaugmentation with an enriched microbial population was applied as treatment for facing transient or continuous shock loads of PNP. The effect of the amount of enriched microbial population added for bioaugmentation was assessed using two different dosages. In the cases tested, total PNP removal was achieved during the transient PNP shock load. However, after a long PNP starvation period, total PNP removal during a second PNP shock load was achieved, when higher doses were applied. Therefore, the dosage of specialized bacteria was established as the key factor for a successful bioaugmentation strategy. This was confirmed with the microbial characterization through fluorescence in-situ hibridisation during experiments. In addition, the performance of a bioaugmented SBR receiving a continuous PNP shock load was enhanced when compared to a non-bioaugmented SBR. Finally, in the case of highly concentrated PNP wastewaters that cannot be degraded in a biological reactor, wet air oxidation (WAO) and catalytic WAO (CWAO) were performed with the aim of increasing the biodegradability prior to a biological remediation. The influence of temperature, oxygen partial pressure, pH, ionic strength and type of catalyst on PNP CWAO was studied. Four Pt and Ru-based catalysts have been tested in batch experiments. PNP elimination, total organic carbon abatement and intermediates distribution were monitored. Respirometric tests were done to assess the biodegradability enhancement of the CWAO effluents. PNP elimination was higher than 90% in most cases. Temperature was the most important operating parameter upon CWAO. Moreover, CWAO increased biodegradability by more than 50% for most of the conditions tested; the best biodegradability enhancement was observed when the carboxylic acids fraction was the highest. An integrated CWAO and biological treatment would allow an easy removal of highly concentrated PNP and the intermediates formed during CWAO step. In conclusion, this research contributed to a deeper understanding of the dynamics of PNP degradation under different technologies and provides an aid to propose a best available technology for the removal of recalcitrant compounds from industrial wastewaters.

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