Cytotoxic and genotoxic activities of waters and sediments from highway and parking lot runoffs.

The genotoxicity of water and sediment samples from stormwater treatment systems and water from urban highway runoff was tested in the Salmonella/microsome assays with Salmonella typhimurium, micronucleus assay (Trad-MN) with plants and with human-derived liver cells (HepG2), or comet assay with HepG2. Cytotoxicity of water samples was studied using either reactive oxygen species (ROS) generation, cell proliferation or dye exclusion assay in HepG2. Concentrations of several contaminants in the tested samples were also measured. Results suggested that urban highway runoff exposed to severe vehicle traffic emissions caused genotoxic effects in comet assay and in Trad-MN assays. Sediments induced either mutagenic effects in strain YG1024 or genotoxic effects in Trad-MN assay. These effects could be due to the presence of nitro-polycyclic aromatic hydrocarbons (NPAHs) which possess carcinogenic and mutagenic properties. Influent and effluents of stormwater treatment systems did not induce genotoxic activity or effects on HepG2 cell viability; however, the influents were able to induce ROS generation and cell proliferation in HepG2 cells. As the methods require a sterile filtration of the water samples, this could have also removed particulate-associated polycyclic aromatic hydrocarbons (PAHs) and resulted in a less pronounced induction of genotoxicity, as would be expected by PAH contamination.

Application of ionic liquids for the removal of heavy metals from wastewater and activated sludge.

This paper presents the results of adsorption studies on the removal of heavy metals (Cr, Cu, Cd, Ni, Pb and Zn) from standard solutions, real wastewater samples and activated sewage sludge using a new technique of liquid-liquid extraction using quaternary ammonium and phosphonium ionic liquids (ILs). Batch sorption experiments were conducted using the ILs [PR4][TS], [PR4][MTBA], [A336][TS] and [A336][MTBA]. Removal of these heavy metals from standard solutions were not effective, however removal of heavy metals from the industrial effluents/wastewater treatment plants were satisfactory, indicating that the removal depends mainly on the composition of the wastewater and cannot be predicted with standard solutions. Removal of heavy metals from activated sludge proved to be more successful than conventional methods such as incineration, acid extraction, thermal treatment, etc. For the heavy metals Cu, Ni and Zn, ≥90% removal was achieved.

Gaseous nitrogen and carbon emissions from a full-scale deammonification plant.

The aim of this work was to give a quantitative description of the gaseous nitrogen and carbon emissions of a full-scale deammonification plant (DEMON system). Deammonification accounted for the net carbon sequestration of 0.16 g CO2/g NO2-N. Both nitrogen dioxide (NO2) and nitric oxide (NO) were minor trace gases (<0.1% nitrogen output). However, in comparison, the nitrous oxide (N2O) emission (1.3% nitrogen output) was significant. The global warming potential of the N2O emissions from the DEMON were similar to those found in conventional simultaneous nitrification/denitrification systems; however, CO2 emissions in the investigated system were significantly lower, thereby lessening the overall environmental effect. This was the first time such an analysis has been performed on a DEMON system.

EU Water Framework Directive and Stockholm Convention: can we reach the targets for priority substances and persistent organic pollutants?

BACKGROUND, AIM AND SCOPE: Water is a renewable resource and acceptable quality is important for human health, ecological and economic reasons, but human activity can cause great damage to the natural aquatic environment. Managing the water cycle in a sustainable way is the key to protect natural resources and human health. On a global level, the microbiological contamination of water sources is a major problem in connection with poverty and the United Nations Millennium Development Declaration is an important initiative to handle this problem. In terms of environmental health, persistent organic pollutants (POPs) circulate globally; as they travel long distances, they are found in remote areas far from their original source of application and can cause damage wherever they move to. On a global scale, United Nations Environmental Programme (UNEP) issued the Stockholm Convention to reduce POPs; in the European Union (EU), one intention of the Water Framework Directive (WFD) is to reach the good chemical status of waters; beside these regulations, there are other directives in support of these goals. The aim of this paper is to discuss whether the Stockholm Convention and the WFD allows meeting the targets of protection of human and environmental health, which are established in the different directives and how could we approach the targets. MATERIALS AND METHODS: The aims and scopes of different directives are compiled and compared with the actual quality of water, different approaches of standard settings are compared and potential treatment options are discussed. RESULTS: Under the Stockholm Convention on POPs, which came into force in May 2004, governments are required to develop a National Implementation Plan (NIP) setting out how they will address their obligations under the convention and how they will take measures to eliminate or reduce the release of POPs into the environment by the use of best available techniques (BAT) and application of best environmental practices (BEP). On a European level, the WFD has been in place as the main European legislation to protect our water resources and the water environment of Europe since 2000. It requires managing river basins so that the quality and quantity of water does not affect the ecological services of any specific water body. Nevertheless, the goals of other directives as for drinking water, bathing water and urban wastewater treatment are not yet harmonised mainly concerning microbiological, priority substances and priority hazardous substances (PS/PHS) contamination. Following the detection of substances, a risk assessment with sound effect data needs to be performed also for regulatory decisions and priorisation of measures to remove emerging contaminants. Beside personal care products and industrial contaminants, faecal pollution of recreational waters is one of the major hazards facing users, although microbial contamination from other sources as well as chemical and physical aspects also affects the suitability of water for recreation. As in arid and semiarid areas, wastewater is considered for irrigation with regulatory needs of hygienic and chemical parameters-health-based targets-to avoid the contamination of crops and food. In surface waters, currently, the relationships between physical and chemical properties and the biological state of surface waters were quite well-understood to enable the management of catchments and rivers to achieve ecological quality. DISCUSSION: Nevertheless, more work is needed to find out the actual impact of the regulations for single chemicals and complex mixtures, in terms of environmental quality standards to achieve a 'good chemical status', on the good biological status. In a next step after the adoption of the list of PS/PHS substances, which also includes the POPs, the Urban Wastewater Treatment Directive (UWWTD) needs to be adjusted and existing or new treatment options (BATs) should comply with the new requirements of the different directives. CONCLUSIONS: Relevant substances threaten human health and the environment by new effects such as CMR, endocrine-disrupting effects or neurotoxicity which are not yet considered in an adequate way by assessment methods and regulatory standards and the application of abatement technologies. The Registration, Evaluation, Authorisation and Restriction of Chemicals helps to control the sources, but WFD, the Stockholm Convention and UWWTD need to be harmonised and a rolling revision process should react on new developments. Finally, to answer the question if the Stockholm Convention and the WFD (2000/60/EC) could reach the target-I would state that they provide a very valuable frame to approach the targets, but there is still way to go to reach them on an EU level and on a global scale, also under the aspects of the Stockholm Convention and the Millennium Development Goals. PERSPECTIVES: The compilation of the goals of different regulations and combined actions will save a lot of administrative efforts and money.

Assessment of cationic surfactants mineralization by ozonation and photo-Fenton process.

Aqueous solutions of two important quaternary ammonium compounds--16-BAC (benzyl-dimethyl-hexadecylammonium-chloride) and 18-BAC (benzyl-dimethyl-stearylammonium-chloride)--were treated by the ozonation and photo-Fenton processes at different ozone doses and hydrogen peroxide concentrations, respectively. During the photo-Fenton experiments, two different types of lamps were used--a UV mercury vapor medium pressure lamp and a xenon lamp, which simulates solar radiation. The total organic carbon removal was monitored to follow the mineralization of the surfactants. According to the experimental results, after 90 minutes of treatment, the photo-Fenton process achieved up to 80% of mineralization when the UV lamp was used. The efficiency of the photo-Fenton with the xenon lamp was lower. The ozonation process reached, at most, 50% mineralization at the used conditions (ozone dose = 7.57 g/h).

Genotoxic effects of wastewater from an oncological ward.

Aim of this study was the evaluation of the genotoxic activities of hospital wastewaters. Samples from an oncological ward of the general hospital of Vienna, Austria, were tested in the Salmonella/microsome assay in strains TA98, TA100 and TA1535 with or without metabolic activation, and in the single-cell gel electrophoresis (SCGE) assay with primary rat hepatocytes. In the bacterial tests, consistently negative results were obtained while in the experiments with liver cells a significant and dose-dependent induction of DNA damage (up to two-fold over the background) was found. Membrane filtration resulted in a substantial (62-77%) reduction of these effects, while additional treatments (activated carbon filtration and UV-irradiation) did not lead to a further decrease of the genotoxic activity of the samples. SCGE experiments with cisplatin, carboplatin and 5-fluorouracil, which were detected in the water samples, showed that these cytostatics cause a significant induction of DNA damage only at concentrations that are substantially higher than those in the native waters. These findings indicate that other chemicals, possibly quaternary ammonium compounds, account for the effects of the hospital wastewaters.

Determination of glyphosate and AMPA in surface and waste water using high-performance ion chromatography coupled to inductively coupled plasma dynamic reaction cell mass spectrometry (HPIC-ICP-DRC-MS).

A novel method employing high-performance cation chromatography in combination with inductively coupled plasma dynamic reaction cell mass spectrometry (ICP-DRC-MS) for the simultaneous determination of the herbicide glyphosate (N-phosphonomethylglycine) and its main metabolite aminomethyl phosphonic acid (AMPA) is presented. P was measured as (31)P(16)O(+) using oxygen as reaction gas. For monitoring the stringent target value of 0.1 µg L(-1) for glyphosate, applicable for drinking and surface water within the EU, a two-step enrichment procedure employing Chelex 100 and AG1-X8 resins was applied prior to HPIC-ICP-MS analysis. The presented approach was validated for surface water, revealing concentrations of 0.67 µg L(-1) glyphosate and 2.8 µg L(-1) AMPA in selected Austrian river water samples. Moreover, investigations at three waste water-treatment plants showed that elimination of the compounds at the present concentration levels was not straightforward. On the contrary, all investigated plant effluents showed significant amounts of both compounds. Concentration levels ranged from 0.5-2 µg L(-1) and 4-14 µg L(-1) for glyphosate and AMPA, respectively.

Fate of cancerostatic platinum compounds in biological wastewater treatment of hospital effluents.

The present work focuses on the fate of two cancerostatic platinum compounds (CPC), cisplatin and carboplatin, as well as of two inorganic platinum compounds, [PtCl(4)](2-) and [PtCl(6)](2-) in biological wastewater treatment. Laboratory experiments modelling adsorption of these compounds onto activated sludge showed promising specific adsorption coefficients K(D) and K(OC) and Freundlich adsorption isotherms. However, the adsorption properties of the investigated substances were differing significantly. Adsorption decreased following the order cisplatin>[PtCl(6)](2-)>[PtCl(4)](2-)>carboplatin. LogK(D)-values were ranging from 2.5 to 4.3 , logK(OC) from 3.0 to 4.7. A pilot membrane bioreactor system (MBR) was installed in a hospital in Vienna and fed with wastewater from the oncologic in-patient treatment ward to investigate CPC-adsorption in a sewage treatment plant. During three monitoring periods Pt-concentrations were measured in the influent (3-250 microg l(-1) Pt) and the effluent (2-150 microgl(-1) Pt) of the treatment plant using ICP-MS. The monitoring periods (duration 30d) revealed elimination efficiencies between 51% and 63% based on averaged weekly input-output budgets. The derived logK(D)-values and logK(OC)-values ranged from 2.4 to 4.8 and from 2.8 to 5.3, respectively. Species analysis using HPLC-ICP-MS proofed that mainly carboplatin was present as intact drug in the influent and--due to low logK(D)--in the effluent of the MBR.

Determination of activated sludge biological activity using model corrected CO2 off-gas data.

Carbon dioxide (CO(2)) online off-gas monitoring is useful to detect changes in biological activity for activated sludge systems especially under limited oxygen conditions like under simultaneous nitrification-denitrification (SND) where respirometric measurements are not applicable. So far, the influence of the bicarbonate system on the liquid-gas transfer of CO(2) prevented the wider use of off-gas CO(2) for monitoring purposes in wastewater treatment. The objective of the paper is to demonstrate a practical method to correct measured off-gas CO(2) as an indicator of biological activity by taking into account pH shifts (resulting in CO(2) release or retention) and changes in influent alkalinity. The simple model is based on the physicochemical system of the bicarbonate/CO(2) equilibrium and the liquid-gas mass transfer for aerated systems. Standard on-line measurements (pH, temperature, flow rates) and periodical alkalinity titration serve as input data to estimate the influence of the carbonate system on the CO(2) off-gas concentrations measured on-line. For a particular plant the CO(2) mass transfer coefficients are derived from measurements compared to the theoretical calculation from oxygen mass transfer. The model estimates the biological carbon dioxide production rate (CPR; heterotrophic activity) by the correction of the measured carbon dioxide transfer rate (CTR; C-flux by the off-gas) with the calculated inorganic carbon dioxide transfer rate (r(F)) considering bicarbonate consumption (autotrophic activity).

NOx monitoring of a simultaneous nitrifying-denitrifying (SND) activated sludge plant at different oxidation reduction potentials.

Simultaneous nitrification-denitrification (SND) allows biological nitrogen removal in a single reactor without separation of the two processes in time or space but requires adapted control strategies (anoxic/aerobic conditions). In this study, the formation of gaseous nitric oxide (NO(G)) and nitrogen dioxide (NO(2G)) was monitored for SND in relation to the oxidation-reduction potential (ORP) and nitrogen removal in a lab batch reactor and a pilot membrane bio-reactor (MBR). In addition hospital wastewater (COD/N(tot)>6:1) was treated on site for 1 year. The highest total nitrogen removal rates of max 90% were reached at 220-240mV ORP (given as E(h)) with corresponding maximal NO(G) emissions rates of 0.9microgg(-1)VSSh(-1). The maximal emission rates of NO(2G) (0.2microgg(-1)VSSh(-1)) were reached at the same ORP level and the NO(2G) emissions correlated to the nitrite accumulation in the activated sludge up to 5mgl(-1)NO(2L)-N. It was shown that this correlation was due to biological production and not due to pH-dependent chemical conversion. Therefore, NO(2G) can be used as additional control loop for ORP-controlled SND systems to avoid the inhibition of denitrification and high nitrite concentrations in the plant effluent.

Development of an analytical method for the determination of anthracyclines in hospital effluents.

Little is known about the fate of cytostatics after their elimination from humans into the environment. Being often very toxic compounds, their quantification in hospital effluents may be necessary to individualise the putative magnitude of pollution problems. We therefore developed a method for the determination of the very important group of anthracyclines (doxorubicin, epirubicin, and daunorubicin) in hospital effluents. Waste water samples were enriched by solid phase extraction (concentration factor 100), analysed by reversed-phase high performance liquid chromatography (RP-HPLC), and monitored by fluorescence detection. This method is reproducible and accurate within a range of 0.1-5 micro g l(-1) for all compounds (limits of quantification: 0.26-0.29 micro g l(-1) ; recoveries >80%). The applicability of the method was proven by chemical analysis of hospital sewage samples (range: 0.1-1.4 micro g l(-1) epirubicin and 0.1-0.5 micro g l(-1) doxorubicin). Obtained over a time period of one month, the results were in line with those calculated by an input-output model. These investigations show that the examined cytostatics are easily detectable and that the presented method is suitable to estimate the dimension of pharmaceutical contamination originating from hospital effluents.

Presence of cancerostatic platinum compounds in hospital wastewater and possible elimination by adsorption to activated sludge.

Platinum originating from the excreted cancerostatic platinum compounds (CPC) cisplatin, carboplatin and oxaliplatin was monitored over a period of 28 days in the wastewater of the oncologic ward of the Vienna University Hospital. Concentration levels ranging from 4.7 to 145 microg L(-1) were measured by inductively coupled plasma mass spectrometry (ICP-MS). An average ratio of weekly drug emission/drug consumption of 0.27+/-0.12 was assessed. Model studies were carried out for fundamental understanding of CPC interaction with the solid phases present at different stages of the water cycle. Wastewater and activated sludge were spiked with CPC at concentration levels as found in the sewer of the oncologic ward. The platinum concentration remaining in the tested solution was measured after 24 h of incubation. Depending on pH, the three substances exhibited considerably different adsorption rates in wastewater. At pH 7, cisplatin was adsorbed by 88%, whereas only 26% of carboplatin and 54% of oxaliplatin were removed from the aqueous phase. Adsorption by activated sludge was higher, less affected by pH variation and comparable for all investigated CPC (96% for cisplatin, 70% for carboplatin and 74% for oxaliplatin at pH 6.8). In a next step, the dependence of CPC adsorption was tested for wastewater and activated sludge of different sampling sites. Strong variations were found only for wastewater, whereas activated sludge showed more consistent elimination rates (average values: cisplatin 92%, carboplatin 72%, and oxaliplatin 78%). These findings indicate that the major part of the excreted CPC is adsorbed by the solid phase in the water cycle and is thus expected to be removed from the wastewater by sewage treatment plants.

Photodegradation of phosphonates in water.

Phosphonates are widely used as chelating agents, e.g., in water cooling systems, in bleaching baths or as scale inhibitors in deflocculation agents. They are considered to be difficult to degrade and produce aminomethylphosphonic acid (AMPA) as a metabolite. As the fate of phosphonates in the environment is not very well known the present work aims at simulating the time dependent photodegradation of four selected phosphonates: nitrilotris-methylenephosphonic acid (NTMP), ethylenediamine-tetra-methylenephosphonic acid (EDTMP), diethylenetriaminepenta-methylenephosphonic acid (DTPMP) and hexaethylenediamine-tetra-methylenephosphonic acid (HDTMP), at concentrations of 1 mg/l (i.e. 3.2 microM NTMP, 2.3 microM EDTMP, 1.7 microM DTPMP and 2.0 microM HDTMP) irradiated by a middle pressure mercury lamp emitting between 190 and 600 nm. The influence of iron under different pH ranges (3, 5-6 and 10) are tested. The degradation of phosphonates is measured by the release of orthophosphates (PO4-P) and aminomethylphosphonic acid (AMPA). This study shows that phosphonates are substances that undergo UV light conversion, which is enhanced in the presence of iron. The half-life without iron is between 15 and 35 min at pH 3, between 10 and 35 min at pH 5-6 and between 50 and 75 min at pH 10. The half-life in the presence of 3.6 microM iron is between 5 and 10 min at pH 3, between 5 and 15 min at pH 5-6 and between 35 and 60 min at pH 10. The individual substances do not significantly influence the reaction rates whereas the presence of iron and the pH have significant effects. The total conversion of phosphonates after 90 min is 75-100% for pH values of 3 and 5-6 and 55-75% for a pH of 10 dependent on the presence of iron. In the environment longer degradation times are to be expected since natural light is weaker by a factor between 125 and 300 in the UVB, a factor between 3 and 8 in the UVA and of the same intensity in the visible range than the light in our study. Although orthophosphates are the major products, AMPA is also shown to be a by-product of the photodegradation of phosphonates that is later converted into orthophosphate.

Novel screening test to assess the potential environmental toxicity of waste water samples.

Biological effects of waste water samples were investigated using the method for isometric contraction measurements that is widely employed in the medical field for studying the effects of various drugs on heart and smooth muscle preparations. Raw waste water samples from a municipal treatment plant were extracted with chloroform and diluted in dimethylsulfoxide. Some samples were also digested with NaOH or microwave. Our results show that the test is sensitive for the investigation of waste water samples. The liquid part of the samples exerted a more potent relaxing effect on terminal ilea than the solids. Alkaline (NaOH) or microwave treated samples showed similar effects as untreated samples. Therefore we conclude that the major part of the reactive agent might be located in the liquid phase. We also demonstrate with this study that the used method enables the screening of waste water samples and their effect on terminal ilea. This method might be a tool to assess the environmental relevance of complex environmental samples.

Determination of 5-fluorouracil in hospital effluents.

Cytostatic anticancer drugs are an increasingly important issue in the environmental debate, mainly due to the lack of knowledge about the fate of these toxic substances. Over the last decades, 5-fluorouracil (5-FU) has been one of the most frequently used antineoplastic agents and may, therefore, be regarded as one of the pilot substances for environmental contamination. As a prerequisite for these investigations, a method for the determination of 5-FU in hospital effluents has been developed. Waste water samples were enriched by solid-phase extraction on ENV(+) columns (concentration factor 500) and analysed by capillary electrophoresis using a buffer containing 80% 160 mM sodium borate buffer (pH 9.5) and 20% acetonitrile (v/v). This method is applicable within the range 5-500 microg 5-FU L(-1). The standard curve (correlation coefficient >0.99) was linear with recovery rates from 80 to 96% and an accuracy from 9.0 to 20% (intra-assay standard deviation 0.7-8.9%; inter-assay standard deviation 2.2-9.5%). Based on the consumption of 5-FU in oncologic departments and the detection limit of 1.7 microg L(-1), this method covers the range necessary to evaluate 5-FU in hospital effluents. The applicability of the method was proven by chemical analysis of real hospital waste water samples. Obtained over a time period of 1 month (range 20-122 microg 5-FU L(-1)), the results were similar to those calculated by an input-output model. The presented method provides an analytical tool necessary to face the monitoring of environmental contamination problems.