MBR technology: a promising approach for the (pre-)treatment of hospital wastewater.

Membrane bioreactor (MBR) technology is a very reliable and extensively tested solution for biological wastewater treatment. Nowadays, separate treatment of highly polluted wastewater streams especially from hospitals and other health care facilities is currently under investigation worldwide. In this context, the MBR technology will play a decisive role because an effluent widely cleaned up from solids and nutrients is absolutely mandatory for a subsequent further elimination of organic trace pollutants. Taking hospital wastewater as an example, the aim of this study was to investigate to what extent MBR technology is an adequate 'pre-treatment' solution for further elimination of trace pollutants. Therefore, we investigated - within a 2-year period - the performance of a full-scale hospital wastewater treatment plant (WWTP) equipped with a MBR by referring to conventional chemical and microbiological standard parameters. Furthermore, we measured the energy consumption and tested different operating conditions. According to our findings the MBR treatment of the hospital wastewater was highly efficient in terms of the removal of solids and nutrients. Finally, we did not observe any major adverse effects on the operation and performance of the MBR system which potentially could derive from the composition of the hospital wastewater. In total, the present study proved that MBR technology is a very efficient and reliable treatment approach for the treatment of highly polluted wastewater from hospitals and can be recommended as a suitable pre-treatment solution for further trace pollutant removal.

The removal and degradation of pharmaceutical compounds during membrane bioreactor treatment.

Pharmaceutical compounds such as non-steroidal anti-inflammatory drugs (NSAIDs) and antibiotics have been detected in sewage treatment plant (STP) effluents, surface and ground water and even in drinking water all over the world, and therefore have developed as compounds of concern. Membrane bioreactor (MBR) treatment has gained significant popularity as an advanced wastewater treatment technology and might be effective for an advanced removal of these pollutants. This paper evaluates the treatment of wastewater containing three NSAIDs (acetaminophen, ketoprofen and naproxen) and three antibiotics (roxithromycin, sulfamethoxazole and trimethoprim) performed in two MBRs with sludge retention times (SRTs) of 15 (MBR-15) and 30 (MBR-30) days over a period of four weeks. It was observed that NSAIDs were removed with higher efficiencies than the antibiotics for both MBRs, and the MBR-30 presented higher removal efficiencies for all the compounds than obtained by MBR-15. Removal rates ranged from 55% (sulfamethoxazole) up to 100% (acetaminophen, ketoprofen). Besides mineralisation biological transformation products of ketoprofen and naproxen produced by wastewater biocoenosis were identified in both MBR permeates using liquid chromatography coupled with mass spectrometry (LC-MS). The results indicated the importance of investigating the environmental fate of pharmaceuticals and their transformation products reaching the environment.

Full scale membrane bioreactor treatment of hospital wastewater as forerunner for hot-spot wastewater treatment solutions in high density urban areas.

Membrane Bioreactors (MBR) are a very attractive option for the treatment of hospital wastewater and elimination of pharmaceuticals in high density urban areas. The present investigation showed that, depending on the substance, between 19% and 94% of the level of antibiotics found in the environment originate from hospitals. Because of their ecotoxic potential, hospital wastewaters can have a significant impact on the environment. The segregation of these wastewaters and their separate treatment at the source can reduce the entry of drugs in waterways and enable water reuse after adequate polishing treatment processes.

Tertiary treatment of slaughterhouse effluent: degradation kinetics applying UV radiation or H2O2/UV.

In some Brazilian regions, surface water has become scarce, e.g. semi arid climate areas and densely populated and industrial areas, where water over-exploitation and/or fluvial pollution has been more common. Advanced oxidative processes (AOP) provide treated water as a source of reuse water even with the characteristics of drinking water enabling water reuse practices also in food industries. The secondary wastewater of a slaughterhouse was the water source for a tertiary treatment study evaluating the kinetics of the photo-induced degradation of color and UV254 under UV radiation with and without the addition of H2O2. The proximity of the k' values of color and UV254 degradation by UV indicates that the compounds responsible for color may be the same content measured by UV254. The H2O2/UV treatment was 5.2 times faster than simple UV in removing aromatic compounds. The degradation kinetics of aromatic compounds in both treatments followed a pseudo-first order law. The pseudo-first order constant for H2O2/UV and UV treatments were kUV254'=0.0306 min(-1) and kUV254'=0.0056 min(-1), respectively.

Generation of endocrine disruptor compounds during ozone treatment of tannery wastewater confirmed by biological effect analysis and substance specific analysis.

Ozone (O3) with its high oxidation potential was used to degrade or eliminate pollutants contained in tannery wastewater when applying different pHs and quantities of O3. Our objective was a chemical degradation by O3 to achieve an enhancement of biodegradability, with a parallel decrease in toxicity. Conventional analyses and bioassays beside substance specific analyses were performed to clear-up the behaviour of wastewater content from tanning process. The results demonstrate that the dominant organic pollutants were chemically degraded by oxidation as the chemical and biochemical oxygen demand (COD and BOD) prove, while changes in carbon content monitored by total or dissolved organic carbon content (TOC or DOC) were only marginal. Vibrio fischeri and Daphnia magna toxicity testing performed in parallel proved a decrease in toxicity after O3-treatment, while the estrogenic activity determined by enzyme-linked receptor assay (ELRA), however, proved an increase of endocrine disruptor compounds (EDC). Results could be explained by substance-specific analyses using gas chromatography (GC-MS) and liquid chromatography/mass spectrometry (LC-MS). From GC-MS analysis the elimination of non-polar compounds could be recognized, whereas the oxidative conversion led to an increase of EDC compounds, which qualitatively could be identified by LC-MS as nonylphenol ethoxylate (NPEO) degradation products: short chain NPEOs, nonylphenol carboxylates (NPECs) and nonylphenol (NP).

Detection and identification of degradation products of sulfamethoxazole by means of LC/MS and -MSn after ozone treatment.

The ozonation of the antibiotic sulfamethoxazole has been studied, in order to elucidate the structures of some of the degradation products generated throughout the process. Under the conditions applied, a complete destruction of sulfamethoxazole was achieved after 10 minutes of reaction. The biodegradability of the resulting solution has been also determined, and this parameter undergoes a gradual increase along during the reaction time. The acute toxicity of the reaction mixture, on the contrary, is only decreased during the first 5 minutes of reaction while it increases subsequently. Some of the intermediates resulting during ozonation seem to be more toxic to Daphnia magna than the untreated sulfamethoxazole. The structures of selected degradation products found in the solution are determined and identified. Ozone predominantly attacks sulfamethoxazole via the amine group of the aniline ring in some cases giving rise to nitro-aromatic compounds.

Evaluation of advanced treatment technologies for the elimination of pharmaceutical compounds.

Pharmaceuticals and their metabolites have developed as ecotoxicologically relevant micropollutants in the aquatic environment. During conventional biological wastewater treatment they are eliminated insufficiently and therefore reach surface waters via discharges. They are either partially or completely non-biodegradable and/or hardly eliminable by activated sludge adsorption because they often have polar structures. Membrane bioreactor treatment (MBR) was applied to pre-treat wastewater containing pharmaceutical compounds, e.g., antibiotics like floxacins and their synthetic precursor compounds. Our objectives were to eliminate these persistent target compounds from wastewater prior to discharge into receiving waters. Therefore an advanced treatment applying MBR combined with different chemical and physicochemical processes was performed. The addition of powdered activated carbon (PAC), nano filtration (NF), reverse osmosis (UO) or ozone (O3) and O3/UV were applied to MBR permeate spiked with the selected target compounds. Treatment efficiency was assessed using conventional inorganic and organic chemical analyses besides advanced physicochemical methods like liquid chromatography coupled with mass and tandem mass spectrometry (LC-MS and -MS-MS).

Contribution to the Detection and Identification of Oxidation Metabolites of Nonylphenol in Sphingomonas sp. strain TTNP3.

Sphingomonas sp. strain TTNP3 has been previously described as a bacterium that is capable of degrading the technical mixture of nonylphenol (NP) isomers and also the 4(3',5'-dimethyl-3'-heptyl)-phenol single isomer of NP. Until recently, 3,5-dimethyl-3-heptanol was the only reported metabolite of 4(3',5'-dimethyl-3'-heptyl)-phenol. A short time ago, the detection of an intracellular metabolite resulting from the oxidation of 4(3',5'-dimethyl-3'-heptyl)-phenol which was identified as 2(3,5-dimethyl-3-heptyl)-benzenediol has been reported. A decisive element for this identification was the occurrence of some slight differences with the two most probable metabolites i.e. 4(3',5'-dimethyl-3'-heptyl)-resorcinol and 4(3',5'-dimethyl-3'-heptyl)-catechol. These facts led us to hypothesise some NIH shift mechanisms explaining the formation of 2(3',5'-dimethyl-3'-heptyl)-benzenediol. In the present work, we describe the steps that led to the detection of these metabolites in the intracellular fraction of Sphingomonas sp. strain TTNP3. The formation of analogous intracellular metabolites resulting from the degradation of the technical mixture of NP is reported. To further elucidate these degradation products, studies were carried out with cells grown with 4(3',5'-dimethyl-3'-heptyl)-phenol as sole carbon source. The description of the syntheses of reference compounds, i.e. 4(3',5'-dimethyl-3'-heptyl)-resorcinol and 4(3',5'-dimethyl-3'-heptyl)-catechol and their comparative analyses with the intermediates of the degradation of 4(3',5'-dimethyl-3'-heptyl)-phenol are presented.

Applicability of Fenton and H2O2/UV reactions in the treatment of tannery wastewaters.

In this paper we evaluated the H2O2/UV and the Fenton's oxidation processes for the treatment of tannery wastewater under different experimental conditions. Efficiencies were judged by the amounts of organic substances degraded or eliminated under these treatment techniques. Daphnia magna and Vibrio fischeri were used to monitor toxicity. Organic compounds contained in the untreated and treated tannery wastewater were determined and identified using substance specific techniques. Gas chromatography-mass spectrometry (GC-MS) in positive electron impact (EI(+)) mode was applied to determine volatile organics. Atmospheric pressure ionization (API) mass (MS) and tandem mass spectrometry (MS-MS) coupled with flow injection analysis (FIA) or liquid chromatography (LC) were used to detect or identify polar organic pollutants. The experimental results indicated that both oxidation processes--H2O2/UV at pH 3 and Fenton at pH 3.5--are able to reduce TOC content by mineralisation of the organic compounds.

Derivatisation of 4-nonylphenol and bisphenol A with halogenated anhydrides.

The aim of this work is to synthesize and characterise the halogenated derivatives of the endocrine disrupting compounds (EDCs) 4-nonylphenol (4-NP) and bisphenol A (BPA). Characterisation was performed after gas chromatographic (GC) separation on-line coupled to mass spectrometric (MS) detector and a Fourier Transform Infrared (FTIR) spectroscopic detector. Further structure elucidation was done applying Nuclear Magnetic Resonance spectroscopy (NMR). Two different approaches for the preparation of derivatives were evaluated. At first trifluoroacetyl derivatives were synthesized by the reaction of trifluoroacetic acid (TFA) anhydride and the EDCs in acetonitrile at a temperature of 50 degrees C for 30 minutes. In a second step the 4-NP was derivatised using trichloroacetic acid anhydride and triethylamine in diethyl ether at 20 degrees C for 30 minutes. After synthesis the halogenated NP and BPA derivatives were characterised applying GC/MS, GC/FTIR and NMR. Three indices for a successful derivatisation were observed: El-GC/MS proved a complete derivatisation presenting a characteristic fragmentation pattern for each derivative. The IR spectra obtained by GC/FTIR after derivatisation and separation confirmed the loss of the phenolic O-H stretching vibration at 3,600 cm(-1) while typical absorptions for halogenated compounds now were observed. The NMR-spectra contained the predicted resonance signals.

Microbial degradation of a single branched isomer of nonylphenol by Sphingomonas TTNP3.

The endocrine disrupting chemical nonylphenol (NP) is a technical product which consists of a complex mixture of nonylphenols with different alkyl side-chain isomers. Since the bio-degradation of each NP isomer may lead to its own range of metabolites, the isolation and identification of transformation products is very difficult. In order to overcome this difficulty, the nonylphenol isomer 4(3',5'-dimethyl-3'-heptyl)-phenol (p353NP) was synthesized, and its degradation by an axenic culture of Sphingomonas TTNP3 was investigated with [ring-U-14C]-labelled and non-labelled p353NP including a time-course study. Radioactive mass balancing resulted in different polar soluble fractions, in insoluble radioactivity associated with biomass, and volatile radioactivity in the form of the mineralization product 14CO2. In the extracellular media, the presence of nonanol corresponding to the nonyl chain of the NP isomer was confirmed and its concentration was determined during the course of fermentation. No other radioactive compounds were detected beside the parent isomer. Radioactive metabolites were only found in the intracellular fraction of S. TTNP3.

Perfluorooctane sulfonate--a quite mobile anionic anthropogenic surfactant, ubiquitously found in the environment.

The biochemical degradation of perfluorooctanesulfonate (PFOS) and perfluorooctanoic acid (PFOA) under aerobic and anaerobic conditions in closed-loop systems was monitored in laboratory scale. Adsorptive effects of these compounds to glass and polypropylene were also examined. Liquid chromatography/mass spectrometry (LC-MS) under negative electrospray (ESI(-)) conditions was applied for determination. Elimination of PFOS was observed under anaerobic conditions whereas aerobic treatment was not effective.

Comparison of different advanced oxidation process to reduce toxicity and mineralisation of tannery wastewater.

Many organic compounds contained in wastewater are resistant to conventional chemical and/or biological treatment. Because of this reason different degradation techniques are studied as an alternative to biological and classical physico-chemical processes. Advanced Oxidation Processes (AOPs) probably have developed to become the best options in the near future. AOP while making use of different reaction systems, are all characterised by the same chemical feature: production of OH radicals (*OH). The versatility of AOPs is also enhanced by the fact that they offer different possibilities for OH radical production, thus allowing them to conform to specific treatment requirements. The main problem with AOPs is their high cost. The application of solar technologies to these processes could help to diminish that problem by reducing the energy consumption required for generating UV radiation. In this work, different AOPs (O3, TiO2/UV, Fenton and H2O2/UV) were examined to treat tannery wastewater or as a pre-treatment step for improving the biodegradation of tannery wastewater, at different pH and dosage of the chemicals. Under certain circumstances retardation in biodegradation and/or an increase in toxicity may be observed within these treatment steps. Two different bioassays (Daphnia magna and Vibrio fischeri) have been used for testing the progress of toxicity during the treatment. In parallel other objectives were to analyse and identify organic compounds present in the untreated wastewater and arising degradation products in AOP treated wastewater samples. For this purpose substance specific techniques, e.g., gas chromatography-mass spectrometry (GC-MS) in positive electron impact (El(+)) mode and atmospheric pressure ionisation (API) in combination with flow injection analysis (FIA) or liquid chromatography-mass and tandem mass spectrometry (LC-MS or LC-MS-MS) were performed.

Elucidation of the behavior of tannery wastewater under advanced oxidation conditions.

Diverse advanced oxidation process (AOP) techniques applying UV, TiO2/UV, O3 and O3/UV were used to degrade pollutants contained in tannery wastewater. The total mineralization of these pollutants is desirable, but it is quite energy consuming and sometimes impossible. Therefore the objective was to achieve an enhancement of biodegradability, preferentially with a decrease in toxicity in parallel. This work demonstrates that the dominant pollutants were chemically degraded by oxidation, while changes in carbon content were only marginal. These results were obtained monitoring the total organic carbon content (TOC), chemical and biochemical oxygen demand (COD and BOD), and substance-specific pollutant content by application of gas chromatography/mass spectrometry (GC-MS) and liquid chromatography/mass spectrometry (LC-MS). Daphnia magna toxicity testing performed in parallel proved a decrease in toxicity after AOP treatment of the tannery wastewater.

Mass spectrometric monitoring of the degradation and elimination efficiency for hardly eliminable and hardly biodegradable polar compounds by membrane bioreactors.

Wastewaters containing or spiked with polar compounds--alkylphenolethoxylates (APEOs) and drugs--were treated in membrane-assisted and conventional biological pilot plants to eliminate these pollutants. Elimination resulting in metabolization or ultimate degradation was pursued by substance-specific analysis applying atmospheric pressure chemical ionization (APCI) in combination with mass and tandem mass spectrometric detection (MS and MS-MS) either in the flow injection (FIA) or liquid chromatographic separation (LC) mode. APEOs were diminished by successive cleavage of polyether chain links resulting in short chain APEOs or alkylphenols (AP), if the biocoenosis was adapted to the compounds. Lipid regulating agents (LRA) were either eliminated completely (etofibrate), metabolized to fenofibratic acid (fenofibrate) or diminished to a minimal extent (bezafibrate). Compared to the membrane microfiltration process the conventional activated sludge process was less successful in both APEO and LRA elimination.