Electro-Oxidation Treatment of Pulp and Paper Mill Circulating Waters and Wastewaters

Interest in water treatment by electrochemical methods has grown in recent years. Electrochemical oxidation has been applied particularly successfully to degrade different organic pollutants and disinfect drinking water. This study summarizes the effectiveness of the electrochemical oxidation technique in inactivating different primary biofilm forming paper mill bacteria as well as sulphide and organic material in pulp and paper mill wastewater in laboratory scale batch experiments. Three different electrodes, borondoped diamond (BDD), mixed metal oxide (MMO) and PbO2, were employed as anodes. The impact on inactivation efficiency of parameters such as current density and initial pH or chloride concentration of synthetic paper machine water was studied. The electrochemical behaviour of the electrodes was investigated by cyclic voltammetry with MMO, BDD and PbO2 electrodes in synthetic paper mill water as also with MMO and stainless steel electrodes with biocides. Some suggestions on the formation of different oxidants and oxidation mechanisms were also presented during the treatment. Aerobic paper mill bacteria species (Deinococcus geothermalis, Pseudoxanthomonas taiwanensis and Meiothermus silvanus) were inactivated effectively (>2 log) at MMO electrodes by current density of 50 mA/cm2 and the time taken three minutes. Increasing current density and initial chloride concentration of paper mill water increased the inactivation rate of Deinococcus geothermalis. The inactivation order of different bacteria species was Meiothermus silvanus > Pseudoxanthomonas taiwanensis > Deinococcus geothermalis. It was observed that inactivation was mainly due to the electrochemically generated chlorine/hypochlorite from chloride present in the water and also residual disinfection by chlorine/hypochlorite occurred. In real paper mill effluent treatment sulphide oxidation was effective with all the different initial concentrations (almost 100% reduction, current density 42.9 mA/cm2) and also anaerobic bacteria inactivation was observed (almost 90% reduction by chloride concentration of 164 mg/L and current density of 42.9 mA/cm2 in five minutes). Organic material removal was not as effective when comparing with other tested techniques, probably due to the relatively low treatment times. Cyclic voltammograms in synthetic paper mill water with stainless steel electrode showed that H2O2 could be degraded to radicals during the cathodic runs. This emphasises strong potential of combined electrochemical treatment with this biocide in bacteria inactivation in paper mill environments.

Tautomerism and Fragmentation of Biologically Active Hetero Atom (O, N)-Containing Acyclic and Cyclic Compounds Under Electron Ionization

In this thesis a total of 86 compounds containing the hetero atoms oxygen and nitrogen were studied under electron ionization mass spectrometry (EIMS). These compounds are biologically active and were synthesized by various research groups. The main attention of this study was paid on the fragmentations related to different tautomeric forms of 2- phenacylpyridines, 2-phenacylquinolines, 8-aryl-3,4-dioxo-2H,8H-6,7-dihydroimidazo- [2,1-c][1,2,4]triazines and aryl- and benzyl-substituted 2,3-dihydroimidazo[1,2-a]pyrimidine-5,7-(1H,6H)-diones. Also regio/stereospecific effects on fragmentations of pyrrolo- and isoindoloquinazolinones and naphthoxazine, naphthpyrrolo-oxazinone and naphthoxazino-benzoxazine derivatives were screened. Results were compared with NMR data, when available. The first part of thesis consists of theory and literature review of different types of tautomerism and fragmentation mechanisms in EIMS. The effects of tautomerism in biological systems are also briefly reviewed. In the second part of the thesis the own results of the author, based on six publications,are discussed. For 2-phenacylpyridines and 2-phenacylquinolines the correlation of different Hammett substituent constants to the relative abundances (RA) or total ion currents (% TIC) of selected ions were investigated. Although it was not possible to assign most of the ions formed unambiguously to the different tautomers, the linear fits of their RAs and % TICs can be related to changing contributions of different tautomeric forms. For dioxoimidazotriazines and imidazopyrimidinediones the effects of substituents were rather weak. The fragmentations were also found useful for obtaining structural information. Some stereoisomeric pairs of pyrrolo- and isoindoloquinazolines and regiomeric pairs of naphtoxazine derivatives showed clear differences in thir mass spectra. Some mechanisms are suggested for their fragmentations.