Identification of relevant micropollutants in Austrian municipal wastewater and their behaviour during wastewater treatment.

The European Union has defined environmental quality standards (EQSs) for surface waters for priority substances and several other pollutants. Furthermore national EQSs for several chemicals are valid in Austria. The study investigated the occurrence of these compounds in municipal wastewater treatment plant (WWTP) effluents. In a first screening of 15 WWTPs relevant substances were identified, which subsequently were monitored in 9 WWTPs over 1 year (every 2 months). Out of 77 substances or groups of substances (including more than 90 substances) 13 were identified as potentially relevant in respect to water pollution and subjected to the monitoring, whereas most other compounds were detected in concentrations far below the respective EQS for surface waters and therefore not further considered. The preselected 13 compounds for monitoring were cadmium (Cd), nickel (Ni), copper (Cu), selenium (Se), zinc (Zn), diuron, polybrominated diphenyl ethers (PBDEs), di(ethyl-hydroxyl)phthalate (DEHP), tributyltin compounds (TBT), nonylphenoles (NP), adsorbable organic halogens (AOX) and the complexing agents ethylenediaminetetraacetic acid (EDTA) as well as nitrilotriacetic acid (NTA). In the effluents of WWTPs the concentrations of the priority substances Cd, NP, TBT and diuron frequently exceeded the respective EQS, whereas the concentrations for DEHP and Ni were below the respective EQS. The effluent concentrations for AOX, EDTA, NTA, Cu, Se and Zn frequently are in the range or above the Austrian EQS for surface waters. Besides diuron and EDTA all compounds are removed at least partially during wastewater treatment and for most substances the removal via the excess sludge is the major removal pathway. For the 13 compounds which were monitored in WWTP effluents population equivalent specific discharges were calculated. Since for many compounds no or only few information is available, these population equivalent specific discharges can be used to assess emissions from municipal WWTPs to surface waters as well as to make a first assessment of the impact of a discharge on surface waters chemical status. Comparing discharges and river pollution on a load basis, the influence of diffuse sources becomes obvious and therefore should also be taken into consideration in river management.

Occurrence of polycyclic musks in wastewater and receiving water bodies and fate during wastewater treatment.

The occurrence of cashmerane (DPMI), celestolide, phantolide, traesolide (ATII), galaxolide (HHCB) and tonalide (AHTN) in sewage and surface waters and their fate during wastewater treatment and anaerobic sludge digestion is investigated. AHTN and HHCB are the most important representatives and influent concentrations of 0.41-1.8 and 0.9-13 µgL(-1) are observed. DPMI is detected in influent and effluent samples but in notably lower concentrations than AHTN and HHCB. Major sources of polycyclic musks are households, whereas industrial emitters seem to be of minor importance. This conclusion is supported by the analysis of selected industrial wastewaters (metal, textile and paper industry). Specific emissions of 0.36 ± 0.19 and 1.6 ± 1.0 mg cap(-1)d(-1) for AHTN and HHCB are calculated. Overall removal efficiencies between approx 50% and more than 95% are observed during biological wastewater treatment and removal with the excess sludge is the major removal pathway. Log K(D) values of 3.73-4.3 for AHTN, 3.87-4.34 for HHCB and 2.42-3.22 for DPMI are observed in secondary sludge. During sludge digestion no or only slight removal occurred. Mean polycyclic musk concentrations in digested sludge amounted to 1.9 ± 0.9 (AHTN), 14.2 ± 5.8 (HHCB), 0.8 ± 0.4 (ATII) and 0.2 ± 0.09 (DPMI) mgkg(-1) dry matter. In the receiving water systems a comparable distribution as during wastewater treatment is observed. AHTN, HHCB and DPMI are detected in surface waters (ND (not detected) - <0.04, ND - 0.32 and ND - 0.02 µg L(-1)) as well as AHTN and HHCB in sediments (ND - 20, ND - 120 µg kg(-1)). For HHCB an apparent K(OC) value of 4.1-4.4 is calculated for sediments. Major source for polycyclic musks in surface waters are discharges from wastewater treatment plants. For HHCB and DPMI 100% of the load observed in the sampled surface waters derive from discharges of treated wastewater.

Second interlaboratory exercise on non-steroidal anti-inflammatory drug analysis in environmental aqueous samples.

Several interlaboratory exercises were organised within the framework of European FP6 project NORMAN. Among others, non-steroidal anti-inflammatory drugs were investigated in different aqueous samples in two sequential ring studies. The aim of both studies was to evaluate the state-of-art in Europe and to determine possible sources of variation, while also attempting to diminish them. In the present paper we discuss the results of the 2nd Interlaboratory study, while the results of 1st round were presented before. The main scope of the 1st exercise organised within NORMAN project was to assess the laboratory proficiency regardless of the analytical method applied, to evaluate the stability of the target compounds during sample storage, and to define possible sources of variation during sample shipment, storage and analysis. In the 2nd round we primarily aimed to diminish these sources of variation by applying two predetermined analytical protocols based on liquid chromatography-mass spectrometry or gas chromatography-mass spectrometry. The two analytical protocols were compared in terms of their ability to determine individual analytes in matrices of different complexity, i.e. tap water, river water and wastewater. Furthermore, the 2nd exercise addressed also the filtration and compared the influence of different filter material categories on the analysis of non-steroidal anti-inflammatory drugs. Results presented herein evaluate laboratory performance using z-score, bias, proximity and Youden plots. Overall, the laboratory performances were found to be satisfactory for determining NSAIDs in aqueous samples. The two analytical protocols, LC-MS and GC-MS, are assessed according to their sensitivity and measurement uncertainty, where the GC-MS proved superior for the analysis of Ibuprofen, Ketoprofen and Naproxen in matrices with higher complexity. Finally, neither the filtration itself, nor the filter materials were shown to significantly affect the determination of NSAIDs.

Occurrence of phthalates in surface runoff, untreated and treated wastewater and fate during wastewater treatment.

Dimethyl phthalate, diethyl phthalate, dibuthyl phthalate, butylbenzyl phthalate, bis(2-ethylbenzyl) phthalate (DEHP) and dioctyl phthalate were analysed in raw and treated wastewater as well as in surface runoff samples from traffic roads. All six investigated phthalates have been detected in all raw sewage samples, in nearly all wastewater treatment plant (WWTP) effluent samples and in all road runoff samples, with DEHP being the most abundant compound. DEHP inflow concentrations ranged 3.4-34 microg L(-1) and effluent concentrations 0.083-6.6 microg L(-1). In two WWTPs the fate of the phthalates was assessed by performing mass balances. Overall removal efficiencies of approx 95% were calculated. Removal is attributed to biotransformation and adsorption and the relevance of the removal via adsorption to sludge increased with increasing molecular weight and increasing lipophilic character of the compound. Except DEHP phthalate concentrations were higher in treated effluent samples than in road runoff. The environmental quality standard (EQS) for DEHP in surface waters is exceeded only in a few effluent samples, whereas nearly all road runoff samples were higher than the EQS. An assessment based on pure concentrations is not feasible and a mass balance based approach is required. Nevertheless the observations highlight the relevance of stormwater emissions and direct emissions from separated sewer systems to surface waters in relation to emissions from WWTPs and the necessity to consider all potential influences in the assessment of the status of surface water bodies with reference to xenobiotics.

Inter-laboratory exercise on steroid estrogens in aqueous samples.

An inter-laboratory comparison exercise was organized among European laboratories, under the aegis of EU COST Action 636: "Xenobiotics in Urban Water Cycle". The objective was to evaluate the performance of testing laboratories determining "Endocrine Disrupting Compounds" (EDC) in various aqueous matrices. As the main task three steroid estrogens: 17alpha-ethinylestradiol, 17beta-estradiol and estrone were determined in four spiked aqueous matrices: tap water, river water and wastewater treatment plant influent and effluent using GC-MS and LC-MS/MS. Results were compared and discussed according to the analytical techniques applied, the accuracy and reproducibility of the analytical methods and the nature of the sample matrices. Overall, the results obtained in this inter-laboratory exercise reveal a high level of competence among the participating laboratories for the detection of steroid estrogens in water samples indicating that GC-MS as well as LC-MS/MS can equally be employed for the analysis of natural and synthetic hormones.

Perfluorinated alkylated substances in the aquatic environment: an Austrian case study.

Perfluorinated alkylated substances (PFAS) are of global interest due to their occurrence and persistency in the environment. This study includes surface waters and sediments for the analysis of eleven PFAS. The PFAS studied can be grouped in perfluoroalkyl carboxylates (PFCAs), perfluoroalkyl sulfonates (PFS) and perfluoroalkyl sulfonamides (PFSA). The two most important compounds are perfluorooctanoate (PFOA) and perfluorooctane sulfonate (PFOS). These two substances showed the most significant values for surface water samples with maximum concentrations of 21 ng l(-1) for PFOA and 37 ng l(-1) for PFOS. Sediment samples from seven Austrian lakes and the river Danube were studied. Whereas PFSA and PFS were not detected in any sediment sample PFCAs were detected in most of the lake samples in concentrations up to 1.7 microg kg(-1) dry wt. PFOA, perfluorohexanoic acid (PFHxA) and perfluoroheptanoic acid (PFHpA) were detected in all Danube river sediment samples in concentrations varying from 0.1 up to 5.1 microg kg(-1) dry wt. For the various sampling points the proportional mass flows deriving from wastewater discharges were calculated. Whereas only up to 10% of the average flow is discharged wastewater up to more than 50% of the PFAS mass flows in the rivers can be attributed to wastewater discharges. Besides wastewater different other pathways as emissions from point sources, further degradation of precursor products, runoff from contaminated sites or surface runoff as well as dry and wet deposition have to be considered as relevant sources for PFAS contamination in surface waters.

Emissions of perfluorinated alkylated substances (PFAS) from point sources--identification of relevant branches.

Effluents of wastewater treatment plants are relevant point sources for the emission of hazardous xenobiotic substances to the aquatic environment. One group of substances, which recently entered scientific and political discussions, is the group of the perfluorinated alkylated substances (PFAS). The most studied compounds from this group are perfluorooctanoic acid (PFOA) and perfluorooctane sulphonate (PFOS), which are the most important degradation products of PFAS. These two substances are known to be persistent, bioaccumulative and toxic (PBT). In the present study, eleven PFAS were investigated in effluents of municipal wastewater treatment plants (WWTP) and in industrial wastewaters. PFOS and PFOA proved to be the dominant compounds in all sampled wastewaters. Concentrations of up to 340 ng/L of PFOS and up to 220 ng/L of PFOA were observed. Besides these two compounds, perfluorohexanoic acid (PFHxA) was also present in nearly all effluents and maximum concentrations of up to 280 ng/L were measured. Only N-ethylperfluorooctane sulphonamide (N-EtPFOSA) and its degradation/metabolisation product perfluorooctane sulphonamide (PFOSA) were either detected below the limit of quantification or were not even detected at all. Beside the effluents of the municipal WWTPs, nine industrial wastewaters from six different industrial branches were also investigated. Significantly, the highest emissions or PFOS were observed from metal industry whereas paper industry showed the highest PFOA emission. Several PFAS, especially perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA), perfluorododecanoic acid (PFDoA) and PFOS are predominantly emitted from industrial sources, with concentrations being a factor of 10 higher than those observed in the municipal WWTP effluents. Perfluorodecane sulphonate (PFDS), N-Et-PFOSA and PFOSA were not detected in any of the sampled industrial point sources.

First interlaboratory exercise on non-steroidal anti-inflammatory drugs analysis in environmental samples.

Comparability of monitoring data are essential for any meaningful assessment and for the management of environmental risks of emerging pollutants. The reliability and comparability of data at European level is often limited, because analytical methods for emerging pollutants are often not fully validated, not harmonized or not suitable for all relevant matrices. This paper describes a collaborative interlaboratory exercise for the analysis of non-steroidal anti-inflammatory drugs (NSAIDs) residues in freshwater and wastewater, held in the framework of the EU project "Network of reference laboratories for monitoring of emerging environmental pollutants" (NORMAN). The NSAID compounds selected in this study were ketoprofen, naproxen, ibuprofen and diclofenac. Thirteen laboratories distributed along nine European Countries (Austria, France, Germany, Greece, Italy, Slovak Republic, Slovenia, Spain, and Switzerland) took part in this exercise, 126 samples were analyzed and a total number of 473 values in duplicate were collected. Samples selected in this study include environmental water (river water and waste water) and artificial water (fortified environmental and distilled water) with different ranges of complexity. Two analytical methods were proposed by the organiser; one is based on the use of solid phase extraction (SPE) followed by liquid chromatography-tandem mass spectrometry (LC-MS/MS) and the second one is based on SPE followed by gas-chromatography-mass spectrometry (GC-MS), however, in the first round some different approaches were also admitted. The main goals of this interlaboratory comparison were to evaluate the available analytical schemes for NSAID analysis in natural waters, to evaluate the repeatability (r) and reproducibility (R) between participating laboratories, and to evaluate the influence of the analytical method and sample matrices on the results.

Occurrence of selected surfactants in untreated and treated sewage.

Several surfactants were monitored in treated and untreated sewage in nine municipal wastewater treatment plants (WWTPs) in western Austria. The nine sampled WWTPs cover a wide variety referring to size and applied treatment technology. The investigation focused on linear alkylbenzene sulphonate (LAS), quaternary ammonia compounds (QAC), nonylphenol (NP), octylphenol (OP), nonylphenolmono- (NP(1)EO) and -diethoxylates (NP(2)EO). Whereas LAS, NP, OP and NP(1,2)EO were analysed separately in the liquid phase and in the solid phase, the QACs were measured in the total sample. Total influent concentrations of LAS varied between 2.4 mg l(-1) up to 6.7 mg l(-1) whereas total effluent concentrations were in the lower microg l(-1) range (11-50 microg l(-1)). Whichever the type of treatment, a clear removal during treatment was observed. Solid liquid distribution coefficients K(d) were calculated for untreated sewage. The calculated K(d) values varied between 1300 and 3900 l kg(-1). OP was of minor importance with total influent concentrations below 1microg l(-1). NP and NP(1,2)EO were present in all analysed influents in concentrations between 1 and 35microg l(-1). Effluent concentrations were notably lower than the measured influent concentrations. K(d) values for NP varied between 500 and 6600 l kg(-1), for NP(1)EO between 800 and 2700 l kg(-1) and for NP(2)EO between 100 and 1800 l kg(-1). From the QACs several alkyl benzyl (BAC), dialkyl (DDAC) and trialkyl (ATAC) ammonium chlorides with varying alkyl chain lengths were analysed. Highest total concentrations in the influents to the WWTPs were observed for the BAC-C12 and the ATAC-C16 homologues. Effluent concentrations were notably lower compared to influent concentrations, indicating removal by adsorption and/or biodegradation. The influence of the removal by adsorption increased with increasing alkyl chain length.

Environmental risk assessment for quaternary ammonium compounds: a case study from Austria.

Quaternary ammonium compounds (QAC) are widely used as disinfectants, biocides, and detergents, among a variety of other applications. The cationic surface-activity of QAC determines their potential to act as a biocide on both target and non-target organisms. This study aims to provide a broad-based environmental risk characterization and evaluation for selected QAC with particular focus on the situation in Austrian rivers. A modular study design was employed involving environmental exposure characterization, QAC fate and effect analysis in wastewater, ecotoxicological effect characterization, and environmental risk evaluation. A wide array of Austrian surface waters and wastewater effluents were screened for the selected key compounds, benzalkonium chlorides and dialkyldimethylammonium chlorides with different C-chain lengths. Ecotoxicological effect characterization was based on both microbiotests for a set of representative aquatic organisms and a literature review. For risk evaluation, the PEC/PNEC ratio was above 1 for some rivers. Notably, small rivers with a high particulate matter were contaminated with QAC in the case of high water incidents. Hence, for the Austrian sites studied, a QAC-derived risk to sensitive aquatic non-target organisms could not be excluded.

Removal of selected pharmaceuticals, fragrances and endocrine disrupting compounds in a membrane bioreactor and conventional wastewater treatment plants.

Eight pharmaceuticals, two polycyclic musk fragrances and nine endocrine disrupting chemicals were analysed in several waste water treatment plants (WWTPs). A membrane bioreactor in pilot scale was operated at different solid retention times (SRTs) and the results obtained are compared to conventional activated sludge plants (CASP) operated at different SRTs. The SRT is an important design parameter and its impact on achievable treatment efficiencies was evaluated. Different behaviours were observed for the different investigated compounds. Some compounds as the antiepileptic drug carbamazepine were not removed in any of the sampled treatment facilities and effluent concentrations in the range of influent concentrations were measured. Other compounds as bisphenol-A, the analgesic ibuprofen or the lipid regulator bezafibrate were nearly completely removed (removal rates >90%). The operation of WWTPs with SRTs suitable for nitrogen removal (SRT>10 days at 10 degrees C) also increases the removal potential regarding selected micropollutants. No differences in treatment efficiencies were detected between the two treatment techniques. As in conventional WWTP also the removal potential of MBRs depends on the SRT. Ultrafiltration membranes do not allow any additional detention of the investigated substances due to size exclusion. However, MBRs achieve a high SRT within a compact reactor. Nonylphenolpolyehtoxylates were removed in higher extend in very low-loaded conventional WWTPs, due to variations of redox conditions, necessary for the degradation of those compounds.

The solids retention time-a suitable design parameter to evaluate the capacity of wastewater treatment plants to remove micropollutants.

Micropollutants as endocrine disrupting compounds (EDC) or pharmaceuticals are of increased interest in water pollution control. Wastewater treatment plant (WWTP) effluents are relevant point sources for residues of these compounds in the aquatic environment. The solids retention time (SRT) is one important parameter for the design of WWTPs, relating to growth rate of microorganisms and to effluent concentrations. If a specific substance is degraded in dependency on the SRT, a critical value for the sludge age can be determined. In WWTPs operating SRTs below this critical value, effluent concentrations in the range of influent concentrations or a distribution according to the adsorption equilibrium have to be expected, whereas in WWTPs operating at SRTs higher than the critical value degradation will occur. Critical SRTs were determined for different micropollutants, indicating that the design criteria based on the sludge age allows an estimation of emissions. Different treatment technologies as conventional activated sludge systems and a membrane bioreactor were considered and no significant differences in the treatment efficiency were detected when operated at comparable SRT. The results of the investigations lead to the conclusion that low effluent concentrations can be achieved in WWTPs operating SRTs higher than 10 days (referred to a temperature of 10 degrees C). This corresponds to the requirements for WWTPs situated in sensitive areas according to the urban wastewater directive of the European Community (91/271/EEC) in moderate climatic zones.

Analysis of nonylphenol polyethoxylates and their metabolites in water samples by high-performance liquid chromatography with electrospray mass spectrometry detection.

Evidence that some alkylphenol polyethoxylates (APEOs) breakdown products are estrogenic has intensified the interest over their environmental and human health effects. Different quantitative methods but one single preparation and extraction method for the analysis of nonylphenol polyethoxylates (NPEOs) and their metabolites in water samples using solid-phase extraction (SPE) and high-performance liquid chromatography (HPLC) with electrospray mass spectrometry detection (ESI-MS), are described. Quantification limits range about the low ng/l for the enrichment of 500 ml water samples and mean recoveries of 70% are achieved. These methods were subsequently applied to water samples coming from Austrian treatment plants.

Carbamazepine, diclofenac, ibuprofen and bezafibrate--investigations on the behaviour of selected pharmaceuticals during wastewater treatment.

Numerous investigations in different European countries observed various pharmaceutically active compounds (PhACs) in notable concentrations in the aquatic environment. Further determinations found the effluents of sewage treatment plants (STPs) to be significant sources for the entry of pharmaceutical residuals to rivers, streams and surface waters. Due to those pathways the knowledge about the elimination of these substances and their behaviour in wastewater treatment plants (WWTP) is elementary for protection of an intact aquatic environment. Since the sludge retention time (SRT) is the most important parameter for the design of STPs, its influence on the reduction rate of these PhACs in the wastewater treatment process was investigated. To study this influence of the SRT on the elimination of PhACs, lab scale plants have been operated with different sludge retention times. The results of the laboratory experiments have been validated analysing various STPs within a wide capacity range and operating at different SRTs. This report describes the determinations observed on the antiepileptic drug Carbamazepine, the two antiphlogistics and analgesics Diclofenac and Ibuprofen and the lipid regulator Bezafibrate.

Monitoring of selected estrogenic hormones and industrial chemicals in groundwaters and surface waters in Austria.

In order to address the Austrian situation concerning endocrine disrupting substances (EDS), a consortium called Austrian Research Cooperation on Endocrine Modulators (ARCEM) was established in 1999. Among several other issues that were investigated, ARCEM monitored more than 400 ground- and surface water samples for selected estrogenic hormones and industrial chemicals. Appropriate analytical methods were established using GC-HRMS for the detection of hormones and LC/MSMS for the detection of industrial chemicals. Since analytical results were forwarded for toxicological assessments within the programme, quantification limits below 0.1 ng/l (ethinyl estradiol) and 10 ng/l (industrial chemicals) were required depending on the NOEL of the individual compound. Results indicate that both hormones and industrial chemicals occur in the selected ground- and surface water sites in detectable concentrations. Three river sites were identified as being charged with noticeable concentrations of EDS. These results were verified by biological indications within the part of the ARCEM programme dealing with bio-indications.

Water Solubilization in Nonionic Microemulsions Stabilized by Grafted Siliconic Emulsifiers.

Microemulsions containing octanol, decanol, or dodecanol as the oil phase and oligomeric, grafted nonionic amphiphiles based on ethoxylated polymethylsiloxanes (Silwets) have been studied. It was demonstrated that significant amounts of water can be solubilized only when the hydrophobic siliconic backbone is very short (trimers). The water solubilization was evaluated using SAXS, DSC, and conductivity measurements. It was found that up to 40 wt% of water can be solubilized in dodecanol and Silwet L-7607 (MW 1000 and 75 wt% ethylene oxide (EO)). Surprisingly, no free water was detected in the aggregate core. All the solubilized water was confined in the vicinity of the interphasal region and froze at -10 degrees C and below. Up to three molecules of water can be associated with each EO headgroup. Based on SAXS measurements, the structural units of the microemulsions were interpreted to be lamellar-like, a form previously found for the related monomeric microemulsions. Copyright 2001 Academic Press.