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The management of the liquid fraction of digestate produced from the anaerobic digestion of biodegradable municipal solid waste is a difficult affair, as its land application is limited due to high ammonium concentrations and the municipal waste that water treatment plants struggle to treat due to high pollutant loads. The amount of leachate and the pollutant load in the leachate produced by landfills usually decreases with the time, which increases the capacity of landfill leachate treatment plants (LLTPs) to treat additional wastewater. In order to solve the above two challenges, the co-treatment of landfill leachate and the liquid fraction of anaerobic digestate in an industrial-scale LLTP was investigated along with the long-term impacts of the liquid fraction of anaerobic digestate on biocoenosis and its impact on LLTP operational expenses. The co-treatment of landfill leachate and liquid fraction of anaerobic digestate was compared to conventional leachate treatment in an industrial-scale LLTP, which included the use of two parallel lanes (Lane-1 and Lane-2). The average nitrogen removal efficiencies in Lane-1 (co-treatment) were 93.4%, 95%, and 92%, respectively, for C/N ratios of 8.7, 8.9, and 9.4. The average nitrogen removal efficiency in Lane-2 (conventional landfill leachate treatment), meanwhile, was 88%, with a C/N ratio of 6.5. The LLTP’s average chemical oxygen demand (COD) removal efficiencies were 63.5%, 81%, and 78% during phases one, two, and three, respectively. As the volume ratios of the liquid fraction of anaerobic digestate increased, selective oxygen uptake rate experiments demonstrated the dominance of heterotrophic bacteria over ammonium and nitrite-oxidising organisms. The inclusion of the liquid fraction of anaerobic digestate during co-treatment did not cause a significant increase in operational resources, i.e., oxygen, the external carbon source, activated carbon, and energy.

Sulfonated reactive azo dyes, such as Reactive Orange 107, are extensively used in textile industries. Conventional wastewater treatment systems are incapable of degrading and decolorizing reactive azo dyes completely from effluents, because of their stability and resistance to aerobic biodegradation. However, reactive azo dyes are degradable under anaerobic conditions by releasing toxic aromatic amines. To clarify reaction mechanisms and the present toxicity, the hydrolyzed Reactive Orange 107 was treated in anaerobic-aerobic two-step batch experiments. Sulfonated transformation products were identified employing coupled ICP-MS and Q-TOF-MS measurements. Suspected screening lists were generated using the EAWAG-BBD. The toxicity of the reactor content was determined utilizing online measurements of the inhibition of Vibrio fischeri. The OCHEM web platform for environmental modeling was instrumental in the estimations of the environmental impact of generated transformation products.

The total dechlorination of chloroacetic acids in aqueous solutions has been achieved using high-frequency sonoelectrochemical methods. Compared to previous studies, the sonoelectrochemical degradation efficiency was found to be dependent on the ultrasonic frequency and electrodes used. Fractional conversions for trichloroacetic acid and its chlorinated by-products higher than 95% and degradation efficiencies higher than 50% were achieved in all cases where high-frequency sonoelectrochemical experiments were conducted in absence of a background electrolyte. The best results were obtained using lead dioxide as anode and steel as cathode, where both the fractional conversion and degradation efficiency resulted higher than 99.5%. The use of the electricity as unique reactant and the appearing mineralization of the trichloroacetic acids and its by-products make the sonoelectrochemical technology a serious alternative to current technologies.

Azo dyes are of synthetic origin and their environmental fate is not well understood. They are resistant to direct aerobic bacterial degradation and form potentially carcinogenic aromatic amines by reduction of the azo group. This study shows that applying the oxidative processes of enzymatic treatment with laccase and ultrasound treatment, both alone and in combination, leads to dye degradation. Laccase treatment degraded both Acid Orange and Direct Blue dyes within 1-5 h but failed in the case of Reactive dyes, whereas ultrasound degraded all the dyes investigated (3-15 h). When applied as multi-stage combinations the treatments showed synergistic effects for dye degradation compared with individual treatments. Bulk light absorption (UV-Vis) and ion pairing HPLC were used for process monitoring. Additionally, mass spectrometry was used to elucidate the structures of intermediates arising from ultrasound treatment.

The study focuses on the Reactive Orange 16 (RO16) degradation products obtained by fungal treatment of the dye. Eighty percent of dye decolorization was achieved within 24 h by Irpex lacteus cultures immobilized on polyurethane foam (PUF). Dye degradation products were investigated using LC–MS analysis. Three compounds were identified as the dye intermediates: 6-acetamido-3,4-dioxo-3,4-dihydronaphthalene-2-sulfonate (m/z 294), (E)-2-(4-acetamidophenyl)-1-carboxyethenesulfonate (m/z 284), and 4-(2-hydroxyethylsulfonyl)phenolate (m/z 201). Despite significant laccase activities detected in the fungal cultures, no backward polymerization of the reaction products resulting in recurrent colorization was observed after fungal treatment of the dye solution.

The sonochemical degradation of the systematically substituted azo compound 2,7-dihydroxy-1-phenylazonaphthaline-3,6-disulfonic acid was investigated using a frequency of 850 kHz and an acoustic input power of 61 W. All derivatives were degraded completely within 6 h by the ultrasonic treatment. Trifluoromethyl substituted azo compounds exhibited 2–3-fold higher degradation rates in comparison to the reference hydrogen substituted azo compound (k = 0.54 h−1). In contrast to enzymatic processes (azoreductase or laccase), the ultrasonic treatment for these ortho-, meta-, and para-substituted azo compound showed 1.5–50-fold higher degradation rates. Additionally the ultrasound treatment was characterized by shorter reaction times. As a result of the detection and identification of specific intermediates using LC-MS a reaction pathway of the sonochemical degradation of the analysed azo compound is proposed indicating the formation of cyclohexadienone and naphthalene quinone derivatives.

A biological high-performance treatment process comprising two 40-L reactor compartments has been developed for purification and decoloration of concentrated textile wastewater containing up to 15 g L(-1) reactive dyestuff. The decoloration rate of 95% meets the requirements of German legislation for textile wastewater treatment. Successful process development and optimization was achieved by use of high-performance liquid chromatography, with diode-array and electrospray tandem mass spectrometric (LC-ESI-MS-MS) detection, coupled with inline microfiltration membrane-sampling devices, applied online to bioreactors as a process analytical tool for the first time. The optimum process performance was found by correlation of dye and decoloration product-specific concentrations with summary properties such as redox potential and dissolved oxygen content. Details of the degradation and decoloration mechanism for the azo dye reactive black 5 was revealed by using mass spectrometry for structure elucidation.

On-line HPLC with diode array detection (DAD) coupled to electrospray tandem mass spectrometry (ESI-MS/MS) is presented as an integrated quality control and process integrated optimisation tool for the continuous monitoring of sulphonated azo dyes (SADs) and their intermediates in anaerobic and aerobic bioprocesses. Ion-pair RP-HPLC is found out to be more suitable for simultaneous monitoring of aromatic amines (AAs), sulphonated aromatic amines (SAAs) and sulphonated azo dyes in comparison to RP-HPLC with polar embedded phases. Monitoring of the anaerobic degradation of the diazo Reactive Black 5 displays the dependency of a two stage azo group reduction mechanism on the redox potential of the bioreactor. An autoxidation sensitive intermediate released from the anaerobic reduction is characterised by ESI-MS/MS for the first time. The functionality of the method is demonstrated by the control and evaluation of selective adaptation of bacteria to certain pollutants and the identification of unknown intermediates causing re-gaining colour released from azo dye treatment.

Power ultrasound of 850 kHz at 60, 90 and 120 W was used for the degradation of industrial azo dyes Acid Orange 5 and 52, Direct Blue 71, Reactive Black 5 and Reactive Orange 16 and 107. The results show that power ultrasound is able to mineralize azo dyes to non-toxic end products, which was confirmed by respiratory inhibition test of Pseudomonas putida. All investigated dyes have been decolorized and degraded within 3-15 h at 90 W and within 1-4 h at 120 W, respectively. Mass spectrometric investigations show, that hydroxyl radicals attack azo dyes by simultaneous azo bond scission, oxidation of nitrogen atoms and hydroxylation of aromatic ring structures. A volumetric scale-up showed a correlation between the energy input and the absolute amount of degraded dye. Up to an energy input of about 90 W no enzymatic deactivation of laccase was observed which might be helpful for a simultaneous action of sonochemical and enzymatic treatments.

Process integrated microfiltration and ultrafiltration based membrane sampling modules were compared by means of HPLC with diode array detection based monitoring of an anaerobic azo dye biodegradation process. The sampling matrix consisted of anaerobic sludge from a municipal wastewater treatment plant. The hydrolysed azo dye Reactive Black 5 (RB5-H) and three products (ionic and nonionic) released from reductive cleavage under anaerobic conditions were continuously monitored by simultaneously separation by ion-pair chromatography. Microfiltration membrane-based sampling showed no retention for any compound observed. Sampling by ultrafiltration significantly retained the observed ionic compounds between 58 and 83% whereas a nonionic compound was not retained. On-line monitoring of an oxygen-sensitive compound was possible whereas off-line detection failed. Robust long time monitoring could be performed for up to 1 week without cleaning the membrane.

A technical solution and development of a method for on-line HPLC monitoring of bioreactor processes in a membrane reactor system are presented. Experiences in system design for the continuous coupling of a bioreactor system with capillary by-pass circuits using membrane flow cells and a dual HPLC system are reported. A continuously working integrated sample purification step by ultrafiltration with the membrane cell coupling is established. Using electrical switching valves and separated pumping and eluent systems, the dual HPLC system allows diode array detection as well as measurement of the refractive index. The application of the on-line HPLC monitoring system is demonstrated by measuring the anaerobic H-acid degradation kinetics. H-acid, 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid, is one of the most important coupling components for a variety of direct, mordant, reactive dyes which remains in the process water and the textile dyeing effluents in high concentration.

Three databases of HPLC retention indices in the 1-nitroalkane scale were recently established (IFM = Institute of Forensic Medicine, MCL = Microchemistry Laboratory, MTSS = Merck Tox Screening System). In two of them (IFM and MTSS) virtually identical chromatographic conditions were applied but different RP-columns. In the third system (MCL) a different column and different elution conditions were used. Among a total of 1149 drugs examined in all three labs, 258 drugs were common for IFM and MTSS, 179 were common for MCL and MTSS, 162 were common for IFM and MCL, and 135 drugs were common for all three databases. Good agreement of retention index values in IFM and MTSS was demonstrated (r2 = 0.9778). The correlations between IFM and MCL and MTSS and MCL data were less strong (r2 = 0.9245 and 0.9339, respectively), due to some deviating results. These deviations concerned mainly substances with pKa values between 1–4 and were probably caused by the differences in the pH of the two mobile phases. ...

An automated precolumn exchange system for on-line solid-phase extraction (OPS-2) coupled to liquid chromatography with photochemical degradation and electrochemical detection was used for the determination of residual amounts of penicillin G, penicillin V, oxacillin, cloxacillin and dicloxacillin. A 5–10-fold increase in sensitivity was obtained when compared with direct UV detection of penicillins at 225 nm. The system is recommended for samples that have received an immunoaffinity clean-up. Analysis of bovine muscle tissue indicated, however, that this procedure could also be suitable for the determination of penicillin G at its maximum residue limit of 50 μg/kg even with conventional solvent partitioning for the first clean-up steps.

Sixteen sulfonated and unsulfonated azo dyes as well as eleven sulfonated and unsulfonated aromatic amines were analyzed and qualitatively characterized by means of pyrolysis gas chromatography/mass spectrometry at different temperatures. Aniline and aminonaphthalene were found to be the dominant pyrolysis products of sulfonated aromatic amines and dyes. Azo dye and dye class specific key compounds such as benzidine, vinyl-p-base and 4-aminoazobenzene could be identified by pyrolysis gas chromatography/mass spectrometry of commercial acid, cationic, direct, reactive and solvent dyes. 500 degrees C was the optimal pyrolysis temperature for most of the pyrolyzed compounds. The method was applied to a dried sample of a textile wastewater concentrate from a dyeing process. Reactive azo dyes of the group of Remazol dyes and anthraquinone dyes could be identified as the major compounds of the sample. The finding of caprolactam (a printing additive) suggests that the wastewater contained effluent from a process of heat-activated printing with reactive dyes. p-Chloraniline, a banned aromatic amine, was identified. Chemical reduction of the wastewater sample prior to pyrolysis resulted in the release of volatile aromatic amines and aided the classification of several products of pyrolysis.

Trametes villosa laccase was used for direct azo dye degradation, and the reaction products that accumulated after 72 h of incubation were analyzed. Liquid chromatography-mass spectrometry (LC-MS) analysis showed the formation of phenolic compounds during the dye oxidation process as well as a large amount of polymerized products that retain azo group integrity. The amino-phenol reactions were also investigated by 13 C-nuclear magnetic resonance and LC-MS analysis, and the polymerization character of laccase was shown. This study highlights the fact that laccases polymerize the reaction products obtained during long-term batch decolorization processes with azo dyes. These polymerized products provide unacceptable color levels in effluents, limiting the application of laccases as bioremediation agents.

The goal of this work was to investigate the decomposition of azo dyes by oxidative methods, such as laccase and ultrasound treatments. Each of these methods has strong and feeble sides. The laccase treatment showed high decolorization rates but cannot degrade all investigated dyes (reactive dyes), and high anionic strength led to enzyme deactivation. Ultrasound treatment can decolorize all tested dyes after 3 h at a high energy input, and prolonged sonication leads to nontoxic ionic species, which was demonstrated by ion chromatography and toxicity assays. For the first time, it was shown that a combination of laccase and ultrasound treatments can have synergistic effects, which was shown by higher degradation rates. Bulk light absorption and ion-pairing high-performance liquid chromatography (IP-HPLC) were used for process monitoring, while with reversed-phase HPLC, a lower number of intermediates than expected by IP-HPLC was found. Liquid chromatography-mass spectrometry indicated that both acid orange dyes lead to a common end product due to laccase treatment. Acid Orange 52 is demethylated by laccase and ultrasound treatment. Further results confirmed that the main effect of ultrasound is based on ˙OH attack on the dye molecules.

Catecholaminergic metabolism in the A1 cell group of the ventrolateral medulla oblongata was followed after application of 3 interoceptive stressfull stimuli by monitoring the extracellular concentration of 3, 4-dihydroxyphenylacetic acid (DOPAC) with an in vivo voltammetric approach. These stimuli provoked an increase of the DOPAC signal with different time course and amplitude. Histamine led to a maximal 200% increase that vanished within two hours. Insulin induced a long-lasting increase of up to 350% that could be reversed by glucose infusion. Electrical stimulation of the sciatic nerve triggered an immediate increase of up to 140% which stopped with the ending of the stimulation. The time-course of this activation is compatible with a possible involvement of catecholaminergic afferents from the A1 group projecting to the paraventricular nucleus in the stimulation of the hypothalamic neurosecretory cells elicited by the stressors.