Evaluation of stormwater micropollutant source control and end-of-pipe control strategies using an uncertainty-calibrated integrated dynamic simulation model.

The estimation of micropollutant (MP) fluxes in stormwater systems is a fundamental prerequisite when preparing strategies to reduce stormwater MP discharges to natural waters. Dynamic integrated models can be important tools in this step, as they can be used to integrate the limited data provided by monitoring campaigns and to evaluate the performance of different strategies based on model simulation results. This study presents an example where six different control strategies, including both source-control and end-of-pipe treatment, were compared. The comparison focused on fluxes of heavy metals (copper, zinc) and organic compounds (fluoranthene). MP fluxes were estimated by using an integrated dynamic model, in combination with stormwater quality measurements. MP sources were identified by using GIS land usage data, runoff quality was simulated by using a conceptual accumulation/washoff model, and a stormwater retention pond was simulated by using a dynamic treatment model based on MP inherent properties. Uncertainty in the results was estimated with a pseudo-Bayesian method. Despite the great uncertainty in the MP fluxes estimated by the runoff quality model, it was possible to compare the six scenarios in terms of discharged MP fluxes, compliance with water quality criteria, and sediment accumulation. Source-control strategies obtained better results in terms of reduction of MP emissions, but all the simulated strategies failed in fulfilling the criteria based on emission limit values. The results presented in this study shows how the efficiency of MP pollution control strategies can be quantified by combining advanced modeling tools (integrated stormwater quality model, uncertainty calibration).

Occurrence and reduction of pharmaceuticals in the water phase at Swedish wastewater treatment plants.

During the last decade, several screening programs for pharmaceuticals at Swedish wastewater treatment plants (WWTPs) have been conducted by research institutes, county councils, and wastewater treatment companies. In this study, influent and effluent concentrations compiled from these screening programs were used to assess the occurrence and reduction of non-antibiotic pharmaceuticals for human usage. The study is limited to full-scale WWTPs with biological treatment. Based on the data compiled, a total of 70 non-antibiotic pharmaceuticals have been detected, at concentrations ranging from a few ng/L to several µg/L, in the influent water. The influent concentrations were compared with the sale volumes and for many pharmaceuticals it was shown that only a small fraction of the amount sold reaches WWTPs as dissolved parent compounds. Pharmaceuticals with low reduction degrees at traditional WWTPs were identified. Further comparison based on the biological treatment showed lower reduction degrees for several pharmaceuticals in trickling filter plants compared with activated sludge plants with nitrogen removal.

Impact of solid retention time and nitrification capacity on the ability of activated sludge to remove pharmaceuticals.

Removal of five acidic pharmaceuticals (ibuprofen, ketoprofen, naproxen, diclofenac and clofibric acid) by activated sludge from five municipal activated sludge treatment processes, with various sludge ages and nitrification capacities, was assessed through batch experiments. The increase in aerobic sludge age from 1-3 to 7 d seemed to be critical for the removal ofnaproxen and ketoprofen, with markedly higher rates of removal at sludge ages of 7 d or more. No removal was shown for diclofenac and clofibric acid, whereas high rates were observed for ibuprofen in all investigated sludges. Parallel examinations of activated sludge batches with and without allylthiourea (12 mg/L), an inhibitor ofammonia monooxygenase, showed minor to moderate influence on the removal rates of ketoprofen and naproxen. These results suggest that the removal rates of biodegradable pharmaceuticals in municipal activated sludge processes are strongly linked to the heterotrophic bacteria community.

Removal of pharmaceuticals in biologically treated wastewater by chlorine dioxide or peracetic acid.

Removal of six active pharmaceutical ingredients in wastewater was investigated using chlorine dioxide (ClO2) or peracetic acid (PAA) as chemical oxidants. Four non-steroidal anti-inflammatory drugs (ibuprofen, naproxen, diclofenac and mefenamic acid) and two lipid-regulating agents (gemfibrozil and clofibric acid, a metabolite of clofibrate) were used as target substances at 40 microg/L initial concentration. Three different wastewaters types originating from two wastewater treatment plants (WWTPs) were used. One wastewater was collected after extended nitrogen removal in activated sludge, one after treatment with high-loaded activated sludge without nitrification, and one from the final effluent from the same plant where nitrogen removal was made in trickling filters for nitrification and moving-bed biofilm reactors for denitrification following the high-loaded plant. Of the six investigated compounds, only clofibric acid and ibuprofen were not removed when treated with ClO2 up to 20 mg/L. With increasing PAA dose up to 50 mg/L, significant removal of most of the pharmaceuticals was observed except for the wastewater with the highest chemical oxygen demand (COD). This indicates that chemical oxidation with ClO2 could be used for tertiary treatment at WWTPs for active pharmaceutical ingredients, whereas PAA was not sufficiently efficient.

Suspended biofilm carrier and activated sludge removal of acidic pharmaceuticals.

Removal of seven active pharmaceutical substances (ibuprofen, ketoprofen, naproxen, diclofenac, clofibric acid, mefenamic acid, and gemfibrozil) was assessed by batch experiments, with suspended biofilm carriers and activated sludge from several full-scale wastewater treatment plants. A distinct difference between nitrifying activated sludge and suspended biofilm carrier removal of several pharmaceuticals was demonstrated. Biofilm carriers from full-scale nitrifying wastewater treatment plants, demonstrated considerably higher removal rates per unit biomass (i.e. suspended solids for the sludges and attached solids for the carriers) of diclofenac, ketoprofen, gemfibrozil, clofibric acid and mefenamic acid compared to the sludges. Among the target pharmaceuticals, only ibuprofen and naproxen showed similar removal rates per unit biomass for the sludges and biofilm carriers. In contrast to the pharmaceutical removal, the nitrification capacity per unit biomass was lower for the carriers than the sludges, which suggests that neither the nitrite nor the ammonia oxidizing bacteria are primarily responsible for the observed differences in pharmaceutical removal. The low ability of ammonia oxidizing bacteria to degrade or transform the target pharmaceuticals was further demonstrated by the limited pharmaceutical removal in an experiment with continuous nitritation and biofilm carriers from a partial nitritation/anammox sludge liquor treatment process.

Quantification of uncertainty in modelled partitioning and removal of heavy metals (Cu, Zn) in a stormwater retention pond and a biofilter.

Strategies for reduction of micropollutant (MP) discharges from stormwater drainage systems require accurate estimation of the potential MP removal in stormwater treatment systems. However, the high uncertainty commonly affecting stormwater runoff quality modelling also influences stormwater treatment models. This study identified the major sources of uncertainty when estimating the removal of copper and zinc in a retention pond and a biofilter by using a conceptual dynamic model which estimates MP partitioning between the dissolved and particulate phases as well as environmental fate based on substance-inherent properties. The two systems differ in their main removal processes (settling and filtration/sorption, respectively) and in the time resolution of the available measurements (composite samples and pollutographs). The most sensitive model factors, identified by using Global Sensitivity Analysis (GSA), were related to the physical characteristics of the simulated systems (flow and water losses) and to the fate processes related to Total Suspended Solids (TSS). The model prediction bounds were estimated by using the Generalized Likelihood Uncertainty Estimation (GLUE) technique. Composite samples and pollutographs produced similar prediction bounds for the pond and the biofilter, suggesting a limited influence of the temporal resolution of samples on the model prediction bounds. GLUE highlighted model structural uncertainty when modelling the biofilter, due to disregard of plant-driven evapotranspiration, underestimation of sorption and neglect of oversaturation with respect to minerals/salts. The results of this study however illustrate the potential for the application of conceptual dynamic fate models base on substance-inherent properties, in combination with available datasets and statistical methods, to estimate the MP removal in different stormwater treatment systems and compare with environmental quality standards targeting the dissolved MP fraction.

Water management in cities of the future using emission control strategies for priority hazardous substances.

Cities of the future face challenges with respect to the quantity and quality of water resources, and multiple managerial options need to be considered in order to safeguard urban surface water quality. In a recently completed project on 'Source control options for reducing emissions of Priority Pollutants' (ScorePP), seven emission control strategies (ECSs) were developed and tested within a semi-hypothetical case city (SHCC) to evaluate their potential to reduce the emission of selected European priority hazardous substances (PHSs) to surface waters. The ECSs included (1) business-as-usual, (2) full implementation of relevant European (EU) directives, (3) ECS2 in combination with voluntary options for household, municipalities and industry, (4) ECS2 combined with industrial treatment and best available technologies (BAT), (5) ECS2 in combination with stormwater and combined sewer overflow treatment, (6) ECS2 in combination with advanced wastewater treatment, and (7) combinations of ECS3-6. The SHCC approach was chosen to facilitate transparency, to allow compensating for data gaps and to decrease the level of uncertainty in the results. The selected PHSs: cadmium (Cd), hexachlorobenzene (HCB), nonylphenol (NP) and pentabromodiphenyl ether (PBDE) differ in their uses and environmental fate and therefore accumulate in surface waters to differing extents in response to the application of alternative ECS. To achieve the required reduction in PHS levels in urban waters the full implementation of existing EU regulation is prioritised and feasible combinations of managerial and technological options (source control and treatment) can be highly relevant for mitigating releases.

Presence of selected priority and personal care substances in an onsite bathroom greywater treatment facility.

In recent years, concerns about climate change and the inefficient use and ongoing pollution of water resources have increased the political motivation to encourage water recycling. This has led to the widespread introduction of water saving measures and to advances in the decentralised treatment and reuse of wastewater. In particular, the treatment and reuse of greywater has received attention, although important information such as greywater substance loadings is still only rarely available. With the implementation of the European Water Framework Directive the focus on controlling and phasing-out Priority/Priority Hazardous Substances (PS/PHS) is growing, and it is vital to know their sources and flows in order to generate sustainable emission control strategies. The main objective of this study was to quantify the concentrations and loads of PS/PHS and personal care substances in bathroom greywater, and to thereby assess the contribution of household activities to municipal wastewater loads for these substances. Nickel and mercury may be sourced substantially from household activities as it shown in the paper that bathroom greywater contributed a significant proportion of the overall load of these substances at the municipal wastewater treatment plant. Organic matter in the influent greywater was found to be principally associated with large particles (>8 µm), however it was the dissolved and small sized particles that were predominantly removed in the treatment.

Dynamic stormwater treatment unit model for micropollutants (STUMP) based on substance inherent properties.

Modelling the removal of micropollutants (MPs) in stormwater treatment systems is essential in a context that is characterized by a general lack of measurements. This paper presents an innovative dynamic model for the prediction of the removal of MPs in stormwater treatment systems (Stormwater Treatment Unit model for Micro Pollutants--STUMP). The model, based on a conceptual model of two-compartment (water and sediment) serial Continuous Stirred-Tank Reactors (CSTRs), can predict the fate of MPs based on their inherent properties, which are often the only information available regarding this kind of substances. The flexible structure of the model can be applied to a wide range of treatment units and substances. Based on the most relevant removal processes (settling, volatilization, sorption, biodegradation, and abiotic degradation), the model allows the dynamic simulation of the MP behaviour in the different compartments of stormwater treatment systems. The model was tested for heavy metals (copper and zinc) and organic substances (benzene and di(2-ethylhexyl)phthalate). The results show that volatilization plays a big role for removal of benzene while the removal of substances with high sorption capacity is mainly driven by settling. The model was proven to be able to predict the importance of the various fate processes for selected substances with different inherent properties. A thorough assessment of the influence of the various fate process parameters will allow a reliable assessment of the treatment performances for a wide range of MPs.

Ozonation of estrogenic chemicals in biologically treated sewage.

The present study shows that ozonation of effluents from municipal wastewater treatment plants (WWTPs) is likely to be a future treatment solution to remove estrogens and xeno-estrogens. The required ozone dose and electrical energy for producing the ozone were determined in two WWTP effluents for removal of 17 estrogenic chemicals. The estrogenic compounds included parabens, industrial phenols, sunscreen chemicals, and steroid estrogens. The obtained values of Electrical Energy per Order (EEOs) for the treatment of the estrogens were in the range 0.14-1.1 kWh/m(3) corresponding to 1.7-14 g O3/m(3). It is furthermore suggested that UV-absorbance is a useful parameter for online control of the ozone dose in a full scale application since the absorbance of the WWTP effluents and the remaining concentration of the estrogens and xeno-estrogens correlated well with the applied ozone dose.

Presence and fate of priority substances in domestic greywater treatment and reuse systems.

A wide range of household sources may potentially contribute to contaminant loads in domestic greywater. The ability of greywater treatment systems to act as emission control barriers for household micropollutants, thereby providing environmental benefits in addition to potable water savings, have not been fully explored. This paper investigates the sources, presence and potential fate of a selection of xenobiotic micropollutants in on-site greywater treatment systems. All of the investigated compounds are listed under the European Water Framework Directive as either "Priority Substances" (PS) or "Priority Hazardous Substances" (PHS). Significant knowledge gaps are identified. A wide range of potential treatment trains are available for greywater treatment and reuse but treatment efficiency data for priority substances and other micropollutants is very limited. Geochemical modelling indicates that PS/PHS removal during treatment is likely to be predominantly due to sludge/solid phase adsorption, with only minor contributions to the water phase. Many PS/PHS are resistant to biodegradation and as the majority of automated greywater treatment plants periodically discharge sludge to the municipal sewerage system, greywater treatment is unlikely to act as a comprehensive PS/PHS emission barrier. Hence, it is important to ensure that other source control options (e.g. eco-labeling, substance substitution, and regulatory controls) for household items continue to be pursued, in order that PS/PHS emissions from these sources are effectively reduced and/or phased out as required under the demands of the European Water Framework Directive.

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.

Substance flow analysis of parabens in Denmark complemented with a survey of presence and frequency in various commodities.

Parabens are commonly used as preservatives due to anti-bactericidal and anti-fungicidal properties and they are ubiquitously present in personal care products, pharmaceuticals, food, industrial and domestic commodities. They are suspected of causing endocrine disrupting effects to aquatic organisms and adverse effects in humans and, thus, it is highly relevant to identify and quantify their sources and transportation pathways in the urban environment. Here a substance flow analysis (SFA) was performed in order to map and comprehend the substances' flow on a national basis. Many household commodities were found to contain parabens; cleaning detergents, slimy toys, and water-based paint. The presence and concentration of parabens are regulated in cosmetics and food. Use of parabens in pharmaceuticals as excipients is documented in Denmark. The import of parabens is increasing; although the number of industrial parabens containing commodities is decreasing and manufacturer reports phase-out of parabens. The vast majority of the paraben containing commodities has a durability of 18-30 months, thus the average lifetime of the paraben stock is perceived to be limited. The inflow was ca. 154 tonnes via pure chemicals and 7.2-73 tonnes via commodities in 2004. This corresponds to an average wastewater concentration of 640-900 microg/L, when excluding discharge to solid waste, soil, biodegradation and metabolism. This is in the same order of magnitudes as can be found in industrial wastewater but higher than that seen in domestic wastewater. The data needed for the SFA is sparse, dispersed, and difficult to access and associated with a great deal of uncertainty.

Estrogenic personal care products in a greywater reuse system.

The occurrence and fate of parabens in a greywater system was assessed. The potential for removal of residual paraben concentrations in effluent greywater with chlorine dioxide was also investigated. The influent to the greywater plant was characterised by considerable variation, with concentrations from below the detection limit to 40 microg/L and the five commonly used parabens in consumer products were frequently detected. After the biological treatment only two paraben were detected with concentration from 65-120 ng/L. Chlorine dioxide treatment of the biologically treated effluent with dosages down to 0.75 mg/L resulted in more than 97% reduction of all parabens. Formation of the by-product chloroform was insignificant from the chlorine dioxide treatment.

Selected stormwater priority pollutants: a European perspective.

The chemical characteristics of stormwater are dependent on the nature of surfaces (roads, roofs etc.) with which it comes into contact during the runoff process as well as natural processes and anthropogenic activities in the catchments. The different types of pollutants may cause problems during utilisation, detention or discharge of stormwater to the environment and may pose specific demands to decentralised treatment. This paper proposes a scientifically justifiable list of selected stormwater priority pollutants (SSPP) to be used, e.g., for evaluation of the chemical risks occurring in different handling strategies. The SSPP-list consists of 25 pollutant parameters including eight of the priority pollutants currently identified in the European Water Framework Directive. It contains general water quality parameters (organic and suspended matter, nutrients and pH); metals (Cd, Cr, Cu, Ni, Pb, Pt and Zn); PAH (naphthalene, pyrene and benzo[a]pyrene); herbicides (pendimethalin, phenmedipham, glyphosate and terbutylazine); and other representative industrially derived compounds (nonylphenol ethoxylates, pentachlorophenol, di(2-ethylhexyl)phthalate, PCB-28 and methyl tert-butyl ether). Tools for flux modelling, enabling calculation of predicted environmental concentrations (PECs), and for ranking the susceptibility of a pollutant to removal within a range of structural stormwater treatment systems or best management practices (BMPs) have been developed, but further work is required to allow all SSPPs to be addressed in the development of future stormwater pollution control measures. In addition, the identified SSPPs should be considered for inclusion in stormwater related monitoring campaigns.

Transfer of hydrophobic contaminants in urban runoff particles to benthic organisms estimated by an in vitro bioaccessibility test.

An in vitro bioaccessibility test was applied for assessing the transfer of polycyclic aromatic hydrocarbons (PAHs) present in road dust, into benthic organisms living in a receiving water body. The road dust is supposed to be urban runoff particles under wet weather conditions. Sodium dodecyl sulfate (SDS) solution was used as a hypothetical gut fluid. Pyrene, fluoranthene and phenanthrene were the main PAH species in the SDS extractable fraction of road dust, as well as the whole extract. Benzo(ghi)perylene showed relatively low concentrations in the SDS extract in spite of a high concentration in the original dust. The PAH composition in benthic organisms (polychaetes) did not correspond with that of the surrounding sediment and the PAHs detected were also detected in high concentrations in the SDS extract of road dust. When testing the toxicity of the extracted contaminants by a standardised algal toxicity test, SDS extracts of a detention pond sediment showed higher toxicity than the pore water of the corresponding sediment. Sediment suspension showed a comparative toxicity with 0.1% SDS extract. From the results, the in vitro bioaccessibility test seems more suitable to evaluate the exposed contaminants than the traditional organic solvent extraction method and the SDS extracted fraction is applicable to toxicity tests reflecting the digestive process.

A methodology for ranking and hazard identification of xenobiotic organic compounds in urban stormwater.

The paper presents a novel methodology (RICH, Ranking and Identification of Chemical Hazards) for ranking and identification of xenobiotic organic compounds of environmental concern in stormwater discharged to surface water. The RICH method is illustrated as a funnel fitted with different filters that sort out problematic and hazardous compounds based on inherent physico-chemical and biological properties. The outcomes of the RICH procedure are separate lists for both water phase and solid phase associated compounds. These lists comprise: a justified list of compounds which can be disregarded in hazard/risk assessments, a justified list of stormwater priority pollutants which must be included in hazard/risk assessments, and a list of compounds which may be present in discharged stormwater, but cannot be evaluated due to lack of data. The procedure was applied to 233 xenobiotic organic chemicals (XOCs) of relevance for stormwater. Of these 233 compounds, 121 compounds were found to be priority pollutants with regard to solids phases (i.e. suspended solids, soil, or sediments) when stormwater is discharged to surface water and 56 compounds were found to be priority pollutants with regard to the water phase. For 11% of the potential stormwater priority pollutants the screening procedure could not be carried out due to lack of data on basic physico-chemical properties and/or data on bioaccumulation, resistance to biodegradation, and ecotoxicity. The tiered approach applied in the RICH procedure and the focus on the phases relevant for monitoring or risk assessment in the aquatic environment refines the list of "compounds of concern" when compared to the outcome of existing classification schemes. In this paper the RICH procedure is focused on effects in the aquatic environment exemplified with xenobiotic organic compounds (XOCs) found in urban stormwater, but it may be transferred to other environmental compartments and problems. Thus, the RICH procedure can be used as a stand-alone tool for selection of potential priority pollutants or it can be integrated in larger priority setting frameworks.

A novel method for evaluating bioavailability of polycyclic aromatic hydrocarbons in sediments of an urban stream.

Hydrophobic organic pollutants in urban wet weather discharges can accumulate in the sediments of receiving waters and may have adverse effects on the ecological system, especially on benthic organisms. Here, a novel method is developed for evaluating the bioavailability of such hydrophobic organic pollutants by considering the digestive guts in deposit-feeding polychaetes. We compared the amount of polycyclic aromatic hydrocarbons (PAHs) extracted by an organic solvent and by sodium dodecyl sulfate (SDS) solution (as a hypothetical digestive gut fluid of polychaetes) and interpreted the ratio of the two values as bioavailability. The sediment extracts were applied to bacterial acute toxicity tests and algal growth inhibition tests. Sediment samples were collected from an urban stream system receiving wet weather discharges. The bioavailability of the total amount of 12 PAHs in the sediments was in the range 14-38% based on the results from the GC/MS determination of the two different extracts. Lower molecular PAHs showed higher bioavailability compared to the higher molecular ones. The sediment extracts were shown to be toxic towards both algae and bacteria. The SDS extracts showed similar or higher toxicity in the two biotests compared to the organic solvent extracts in spite of their lower PAHs content.

Chemical hazard identification and assessment tool for evaluation of stormwater priority pollutants.

Assessment of chemical hazards is a critical issue, which have to be dealt with when evaluating different strategies for sustainable handling of stormwater. In the present study, a methodology for identifying the most critical and representative chemical pollutants was developed. A list of selected stormwater priority pollutants (SSPP-list) is the out-put from the procedure. Two different strategies for handling of stormwater were considered; discharge into a surface water recipient and infiltration. However, the same methodology can be used for other types of wastewater and other strategies for handling and treatment. A literature survey revealed that at least 656 xenobiotic organic compounds (XOCs) could be present in stormwater. In the next step, 233 XOCs were evaluated with respect to the potential for being hazardous towards either aquatic living organisms or humans, or causing technical or aesthetical problems. 121 XOCs were found have at least one of these negative effects, while 26 XOCs could not be assessed due to the lack of data. The hazard assessment showed that 40 XOCs had a PEC/PNEC ratio above one., e.g. they should be considered as priority pollutants. The final step is the expert judgement, which resulted in a final SSPP-list containing 16 selected priority pollutants.