H. Fr. Schröder

Nonylphenols, nonylphenol-ethoxylates, linear alkylbenzenesulfonates (LAS) and bis (4-chlorophenyl)-sulfone in the German Bight of the North Sea

Nonylphenols and nonylphenol-ethoxylates were detected in the water and sediment samples from the German Bight of the North Sea. Additionally bis (4-chlorophenyl)-sulfone and linear alkylbenzenesulfonates (LAS) were detected in marine waters. Proof of identification is given by comparison of spectral and chromatographic data from the compounds in sample extracts to those obtained from pure standards. In extracts obtained from water samples taken in 1990 and 1995 the concentrations of nonylphenols and bis-(4-chlorophenyl)-sulfone were compared for each year. The concentrations of nonylphenols in seawater varied from 0.7 to 4.4 ng/l while in the Elbe estuary about 33 ng/l were found. In water samples taken in 1998 nonylphenol-polyethoxylates could not be determined, whereas LAS concentrations of 30 ng/l were confirmed by HPLC-MS/MS. The concentrations of bis (4-chlorophenyl)-sulfone ranged from 0.18 to 2.2 ng/l. In sediment samples LAS concentrations of 39-109 ng/g dry weight were determined.

Surfactants : non-biodegradable, significant pollutants in sewage treatment plant effluents : separation, identification and quantification by liquid chromatography, flow-injection analysis-mass spectrometry and tandem mass spectrometry

Abstract Effluents from biological waste water treatment plants contain mainly non-biodegradable polar compounds. Methods for the detection, identification and determination of these hardly or non-eliminatable polar organic compounds are described. Flow-injection analysis (FIA) and liquid chromatographic (LC) separation on an analytical column by mass spectrometric (MS) and tandem mass spectrometric (MS-MS) detection coupled by a thermospray (TSP) interface were performed. The results showed that non-ionic surfactants and their metabolites (primary degradation products) besides linear alkyl benzene sulphonates (LABS) may dominate the range of pollutants. LC-MS confirmed that retention time shifts may occur if waste water extracts are separated on analytical columns. This cannot be recognized by UV detection. The identification of a biochemical degradation product of a non-ionic surfactant was carried out by both FIA-MS-MS and LC-MS-MS. Quantification of this compound was performed by standard addition analysis using FIA-MS or LC-MS in the selected-ion monitoring (SIM) mode. The time required for quantification is 25–30 times higher using LC-MS instead of FIA-MS.

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.

Polar, hydrophilic compounds in drinking water produced from surface water. Determination by liquid chromatography-mass spectrometry.

Drinking water produced from surface water may contain many polar, hydrophilic compounds in spite of different treatment steps such as soil filtration, ozone treatment and activated carbon filtration. Little is known about these compounds. The objectives of this work were the detection and identification by means of tandem mass spectrometry (MS-MS) coupled on-line by a thermospray interface with liquid chromatography. Quantification is possible if standard compounds are available. The different compounds in the water extracts were not only separated by means of an analytical column but also using MS-MS after loop injection bypassing the analytical column. Molecular weight information in the loop spectra (overview spectra) and collisionally induced dissociation (CID) made possible the identification of some of these compounds which cannot be eliminated in the drinking water treatment process. Identification was not only done by interpretation of the recorded daughter- and parent-ion spectra but also by comparing them with a laboratory-made daughter-ion library of polar, hydrophilic pollutants. Direct mixture analysis using MS-MS allows the detection and identification of some of the pollutants if they reach the drinking water in the course of the surface water treatment process because of their biochemical and chemical persistence and/or non-sorbability during the soil or activated carbon filtration process. The proposed method for the analysis of water for polar, non-volatile and/or thermolabile organic substances is a quick, specific and powerful technique which makes it possible to detect and identify these substances without any chromatographic separation or derivatization

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.

Substance-specific detection and pursuit of non-eliminable compounds during biological treatment of waste water from the pharmaceutical industry

Up to now comprehensive examination and assessment of the elimination behaviour of many different pollutants in biological waste water treatment failed above all because of limited possibilities to pursue polar organic compounds of anthropogenic and biogenic origin. In this case the behaviour of waste water constituents during the treatment of waste water from the pharmaceutical industry was studied with the help of mass-spectrometric detection (MS). After completest possible extraction and concentration by liquid/liquid and solid phase extraction (SPE) from samples of influent and effluent of a pilot plant, substance-specific determination and identification was done after chromatographic separation and with the help of mixture analysis, respectively. Separation by gas chromatography coupled with MS was applied to pursue the organic compounds, which are volatile without decomposition, during the waste water treatment process. Flow injection analysis (FIA) bypassing the analytical column combined with soft-ionizing interfaces served for screening of the polar compounds. Then they were separated by liquid chromatographic methods to recognize changes in the qualitative and quantitative compound spectrum. Mixture analysis by FIA combined with tandem mass spectrometry (FIA/MS/MS) was used for identification of the pollutants without previous chromatographic separation. A laboratory-made daughter ion library helped to identify some of the poorly eliminable pollutants detected. The presentation of the monitoring procedures applied was made in such a way that the treatment results were visually recognizable. Due to the use of time-saving FIA/MS, this method may serve for substance-specific monitoring of the treatment of possibly problematic waste waters. ©

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.

Inter-laboratory comparison of liquid chromatographic techniques and enzyme-linked immunosorbent assay for the determination of surfactants in wastewaters.

Seven laboratories participated in an inter-laboratory comparison exercise within the framework of the PRISTINE, SANDRINE and INEXsPORT European Union Projects. Solid-phase extraction (SPE) methodologies were used for the extraction of target analytes from wastewaters. The analytical strategies were based on liquid chromatography (LC) coupled to mass spectrometric (MS) or to fluorescent (FL) detection in all cases with the exception of one laboratory using a test-tube enzyme-linked immunosorbent assay kit. Samples were spiked with the surfactants nonylphenolpolyglycol ether, coconut diethanolamide, linear alkylbenzene sulfonate, nonylphenolpolyglycol ether sulfate, alkylpolyglycol ether and secondary alkane sulfonate. After enrichment on previously conditioned SPE cartridges, the SPE cartridges were distributed among the participating laboratories without the information about the amount of spiked surfactants. In addition, SPE cartridges loaded with a real-world environmental sample containing a tannery wastewater were also analyzed. The results of the programme showed that SPE followed by LC-MS techniques are reliable for the surfactants determination at submicrogram to microgram per liter levels in wastewaters. Inter-laboratory precision values were calculated as the reproducibility relative standard deviation (RSD(R)) which was determined from the reproducibility standard deviation (sR) and the average concentration at a particular concentration level. When data from all laboratories were pooled, the RSD(R) values ranged from 5.1 to 28.3% for the determination of target analytes. The most accurate result corresponded to that given for linear alkylbenzene sulfonates. Taking into account that different methodologies were used (including non-chromatographic techniques) and the complexity of the samples analyzed, it can be considered that acceptable reproducibility values were obtained in this inter-laboratory study.

Physicochemical and Advanced Oxidation Processes – A Comparison of Elimination Results of Antibiotic Compounds Following an MBR Treatment

The occurrence of pharmaceuticals in the environment has become a subject of concern in recent years. A vast number of these compounds have been detected in sewage treatment plants (STP) effluents, surface waters and, less frequently, in ground and drinking water all over the world. Adverse effects caused by pharmaceuticals include aquatic toxicity, resistance development in pathogenic bacteria, genotoxicity and endocrine disruption. Nowadays, it is widely accepted that the main source of pharmaceutical pollution in the aquatic environment are STPs effluents. Therefore, the discharge of pharmaceutical residues with the effluents of STPs should be minimized as far as possible. Degradation of persistent organic pollutants such as pharmaceuticals in water and wastewater can be achieved using advanced treatment technologies such as membrane bioreactors (MBRs) in combination with advanced oxidation processes (AOPS). This paper evaluates the treatment of three antibiotics of large consumption rates worldwide (roxithromycin, sulfamethoxazole and trimethoprim) by MBR followed by different AOP-steps. The identification and quantification of the precursor compounds and degradation products observable during the different treatment steps applied were performed with liquid chromatography coupled with high resolution mass spectrometry (LC-MS)

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).