Selection of organic process and source indicator substances for the anthropogenically influenced water cycle.

An increasing number of organic micropollutants (OMP) is detected in anthropogenically influenced water cycles. Source control and effective natural and technical barriers are essential to maintain a high quality of drinking water resources under these circumstances. Based on the literature and our own research this study proposes a limited number of OMP that can serve as indicator substances for the major sources of OMP, such as wastewater treatment plants, agriculture and surface runoff. Furthermore functional indicators are proposed that allow assessment of the proper function of natural and technical barriers in the aquatic environment, namely conventional municipal wastewater treatment, advanced treatment (ozonation, activated carbon), bank filtration and soil aquifer treatment as well as self-purification in surface water. These indicator substances include the artificial sweetener acesulfame, the anti-inflammatory drug ibuprofen, the anticonvulsant carbamazepine, the corrosion inhibitor benzotriazole and the herbicide mecoprop among others. The chemical indicator substances are intended to support comparisons between watersheds and technical and natural processes independent of specific water cycles and to reduce efforts and costs of chemical analyses without losing essential information.

Search for over 2000 current and legacy micropollutants on a wastewater infiltration site with a UPLC-high resolution MS target screening method.

A target screening method using ultra high performance liquid chromatography-high resolution mass spectrometry (UPLC-HRMS) was developed. The method was applied to 14 groundwater and 11 surface water samples of a former wastewater infiltration site, where raw wastewater was applied until 1985 and treated wastewater is applied since 2005. The measured data are compared with mass spectrometric data of over 2000 organic micropollutants (OMPs), including pharmaceuticals, personal care products, pesticides, industrial chemicals and metabolites of these classes. A total number of 151 and 159 OMPs were detected in groundwater and surface water, respectively, of which 12 have not been reported before in these matrices. Among these 12 compounds were 11 pharmaceuticals and one personal care product. The identity of 55 of the detected OMPs (35%) was verified by analysis of standard compounds. Based on the distribution in the study area, two groups of OMPs were clearly distinguished: current OMPs introduced with treated municipal wastewater since 2005 and legacy OMPs originating from infiltration of untreated wastewater until 1985. A third group included OMPs contained in historic as well as in current wastewater. During infiltration, OMPs with molecular mass >500 g/mol and log DOW > 3.9 were preferentially removed. Speciation had a strong impact with cationic OMPs showing high, neutral OMPs medium and anionic OMPs lowest elimination during infiltration. This target screening method proved useful to study a wide range of compounds, even in retrospect and at sites with poorly documented history and with a complex and variable hydrological situation.

Estimating organic micro-pollutant removal potential of activated carbons using UV absorption and carbon characteristics.

Eight commercially available powdered activated carbons (PAC) were examined regarding organic micro-pollutant (OMP) removal efficiencies in wastewater treatment plant (WWTP) effluent. PAC characteristic numbers such as B.E.T. surface, iodine number and nitrobenzene number were checked for their potential to predict the OMP removal of the PAC products. Furthermore, the PAC-induced removal of UV254 nm absorption (UVA254) in WWTP effluent was determined and also correlated with OMP removal. None of the PAC characteristic numbers can satisfactorily describe OMP removal and accordingly, these characteristics have little informative value on the reduction of OMP concentrations in WWTP effluent. In contrast, UVA254 removal and OMP removal correlate well for carbamazepine, diclofenac, and several iodinated x-ray contrast media. Also, UVA254 removal can roughly describe the average OMP removal of all measured OMP, and can accordingly predict PAC performance in OMP removal. We therefore suggest UVA254 as a handy indicator for the approximation of OMP removal in practical applications where direct OMP concentration quantification is not always available. In continuous operation of large-scale plants, this approach allows for the efficient adjustment of PAC dosing to UVA254, in order to ensure reliable OMP removal whilst minimizing PAC consumption.

Fate of para-toluenesulfonamide (p-TSA) in groundwater under anoxic conditions: modelling results from a field site in Berlin (Germany).

This article reports on a field modelling study to investigate the processes controlling the plume evolution of para-toluenesulfonamide (p-TSA) in anoxic groundwater in Berlin, Germany. The organic contaminant p-TSA originates from the industrial production process of plasticisers, pesticides, antiseptics and drugs and is of general environmental concern for urban water management. Previous laboratory studies revealed that p-TSA is degradable under oxic conditions, whereas it appears to behave conservatively in the absence of oxygen (O2). p-TSA is ubiquitous in the aquatic environment of Berlin and present in high concentrations (up to 38 µg L(-1)) in an anoxic aquifer downgradient of a former sewage farm, where groundwater is partly used for drinking water production. To obtain refined knowledge of p-TSA transport and degradation in an aquifer at field scale, measurements of p-TSA were carried out at 11 locations (at different depths) between 2005 and 2010. Comparison of chloride (Cl(-)) and p-TSA field data showed that p-TSA has been retarded in the same manner as Cl(-). To verify the transport behaviour under field conditions, a two-dimensional transport model was setup, applying the dual-domain mass transfer approach in the model sector corresponding to an area of high aquifer heterogeneity. The distribution of Cl(-) and p-TSA concentrations from the site was reproduced well, confirming that both compounds behave conservatively and are subjected to retardation due to back diffusion from water stagnant zones. Predictive simulations showed that without any remediation measures, the groundwater quality near the drinking water well galleries will be affected by high p-TSA loads for about a hundred years.

Multiresidue analytical method for the simultaneous determination of 72 micropollutants in aqueous samples with ultra high performance liquid chromatography-high resolution mass spectrometry.

A multiresidue method for the simultaneous quantification of 72 micropollutants in aqueous samples by ultra high performance liquid chromatography-high resolution mass spectrometry (UHPLC-HRMS) is described. A variety of substance classes like industrial chemicals, analgesics, anticonvulsants, antihypertensives, psychoactive substances, flame retardants, neutral and acidic pesticides are comprised. A sample volume of 1 mL was enriched by online solid phase extraction (SPE), separated on a 2.6 µm core-shell column and detected with an Exactive™ high resolution mass spectrometer. Simultaneous determination of compounds with different ionization behavior was achieved by polarity switching. One complete run lasted 15 min. The method was validated in the matrices drinking water (DW), diluted surface water (dSW) and diluted waste water treatment plant effluent (dWW) by analyzing 10 replicates spiked at two concentration levels. Limits of quantification (LOQs) ranged between 0.01 and 0.06 µg/L in DW, 0.03 and 0.38 µg/L in dSW, 0.06 and 0.38 µg/L in dWW. The accuracies were between 77 and 117% in DW, 70 and 121% in dSW, 71 and 121% in dWW for both spike levels, respectively. Five compounds in dSW and one compound in dWW were affected by matrix effects, leading to accuracies outside the ranges stated above. The precision for level 2 was excellent with relative standard deviations (RSDs) between 2.2 and 6.5% in DW, 0.5 and 4.9% in dSW and between 1.2 and 6.6% in dWW.

Seeking a compromise between pharmaceutical pollution and phosphorus load: Management strategies for Lake Tegel, Berlin.

Lake Tegel (Berlin, Germany) is controlled by two main inflows: inflow #1 (River Havel) is heavily phosphorus-laden, whereas inflow #2 is an artificial confluence that includes discharge from a municipal wastewater treatment plant distinguished by high levels of phosphorus and pharmaceuticals. To reduce the phosphorus load on the lake, a phosphorus elimination plant (PEP) is situated at inflow #2. Moreover, the two inflows are short-circuited by a pipeline that transfers part of the inflow #1 water to the PEP and finally releases it into inflow #2. The pipeline and the PEP have contributed to a continuous reduction in the total phosphorus concentration of Lake Tegel in the past 25 years. We investigate the question of whether the existing lake pipeline can also be used to reduce the amount of pharmaceuticals in Lake Tegel originating from inflow #2 by dilution with water from River Havel, by diverting part of inflow #2 around the lake, or by a combination of both strategies. The circulation pattern of Lake Tegel is complicated by complex bathymetry and numerous islands and is therefore highly sensitive to winds. We tested seven different management scenarios by hydrodynamic modeling for a period of 16 years with the two-dimensional version of the Princeton Ocean Model (POM). None of the scenarios provided a strategy optimal for both pharmaceuticals and phosphorus. Nonetheless, compound regimes, such as alternating the pipe flow direction or adding another pipeline, allowed the most abundant pharmaceutical (carbamazepine) to be reduced while maintaining the current phosphorus level. This study demonstrates the ability of immediate lake regulation measures to maintain water quality. In the case of Lake Tegel, the pipeline can be fully effective with regard to pharmaceuticals only in combination with additional efforts such as advanced pharmaceutical treatment of wastewater and/or phosphorus reduction in the River Havel catchment.

Occurrence of psychoactive compounds and their metabolites in groundwater downgradient of a decommissioned sewage farm in Berlin (Germany).

PURPOSE: Psychoactive compounds-meprobamate, pyrithyldione, primidone, and its metabolites, phenobarbital, and phenylethylmalonamide-were detected in groundwater within the catchment area of a drinking water treatment plant located downgradient of a former sewage farm in Berlin, Germany. The aim of this study was to investigate the distribution of the psychoactive compounds in anoxic groundwater and to assess the risk of drinking water contamination. Groundwater age was determined to achieve a better understanding of present hydrogeological conditions. METHODS: A large number of observation and production wells were sampled. Samples were analyzed using solid-phase extraction and ultrahigh-performance liquid chromatography-tandem mass spectrometry. Groundwater age was estimated using the helium-tritium ((3)He-(3)H) dating method. RESULTS: Concentrations of psychoactive compounds up to 1 µg/L were encountered in the contamination plume. Generally, concentrations of phenobarbital and meprobamate were the highest. Elevated concentrations of the analytes were also detected in raw water from abstraction wells located approximately 2.5 km downgradient of the former sewage farm. Concentrations in the final drinking water were below the limit of quantification owing to dilution. The age of shallow groundwater samples ranged from years to a decade, whereas groundwater was up to four decades old at 40 m below ground. Concentrations of the compounds increased with groundwater age. CONCLUSIONS: Elevated concentrations of psychoactive drugs indicate a strong persistence of these compounds in the environment under anoxic aquifer conditions. Results suggest that the heritage of sewage irrigation will affect raw water quality in the area for decades. Therefore, further monitoring of raw and final drinking water is recommended to ensure that contaminant concentrations remain below the health-based precautionary value.

Removal kinetics of organic compounds and sum parameters under field conditions for managed aquifer recharge.

Managed aquifer recharge (MAR) provides efficient removal for many organic compounds and sum parameters. However, observed in situ removal efficiencies tend to scatter and cannot be predicted easily. In this paper, a method is introduced which allows to identify and eliminate biased samples and to quantify simultaneously the impact of (i) redox conditions (ii) kinetics (iii) residual threshold values below which no removal occurs and (iv) field site specifics. It enables to rule out spurious correlations between these factors and therefore improves the predictive power. The method is applied to an extensive database from three MAR field sites which was compiled in the NASRI project (2002-2005, Berlin, Germany). Removal characteristics for 38 organic parameters are obtained, of which 9 are analysed independently in 2 different laboratories. Out of these parameters, mainly pharmaceutically active compounds (PhAC) but also sum parameters and industrial chemicals, four compounds are shown to be readily removable whereas six are persistent. All partly removable compounds show a redox dependency and most of them reveal either kinetic dependencies or residual threshold values, which are determined. Differing removal efficiencies at different field sites can usually be explained by characteristics (i) to (iii).

Modelling the removal of p-TSA (para-toluenesulfonamide) during rapid sand filtration used for drinking water treatment.

A finite element model was set-up to determine degradation rate constants for p-TSA during rapid sand filtration (RSF). Data used for the model originated from a column experiment carried out in the filter hall of a drinking water treatment plant in Berlin (Germany). Aerated abstracted groundwater was passed through a 1.6m long column-shaped experimental sand filter applying infiltration rates from 2 to 6mh(-1). Model results were fitted to measured profiles and breakthrough curves of p-TSA for different infiltration rates using both first-order reaction kinetics and Michaelis-Menten kinetics. Both approaches showed that degradation rates varied both in space and time. Higher degradation rates were observed in the upper part of the column, probably related to higher microbial activity in this zone. Measured and simulated breakthrough curves revealed an adaption phase with lower degradation rates after infiltration rates were changed, followed by an adapted phase with more elevated degradation rates. Irrespective of the mathematical approach and the infiltration rate, degradation rates were very high, probably owing to the fact that filter sands have been in operation for decades, receiving high p-TSA concentrations with the raw water.

Behaviour and redox sensitivity of antimicrobial residues during bank filtration.

The behaviour of residues of antibiotic drugs during bank filtration was studied at a field site in Berlin, Germany, where bank-filtered water is used for the production of drinking water. The neighbouring surface water used for bank filtration is under the influence of treated municipal wastewater. Seven out of 19 investigated antimicrobial residues were found in the surface water with median concentrations between 7 and 151ngL(-1). Out of the seven analytes detected in the surface water only three (anhydroerythromycin, clindamycin and sulfamethoxazole) were found with median concentrations above their limits of quantitation in bank filtrate with a travel time of one month or less. With the exception of sulfamethoxazole, none of the 19 analytes were present in bank filtrate with a residence time larger than one month or in the water-supply well itself. Sulfamethoxazole found with a median concentration of 151ngL(-1) in the surface water was the most persistent of all antimicrobial residues. Nevertheless, it was also removed by more than 98% and only found with a median concentration of 2ngL(-1) in the water-supply well. The degradation of clindamycin and sulfamethoxazole appear to be redox-dependent. Clindamycin was eliminated more efficiently under oxic infiltration conditions while sulfamethoxazole was eliminated more rapidly under anoxic infiltration conditions. A slight preference for an improved degradation under oxic (clarithromycin and roxithromycin) or anoxic (anhydroerythromycin) conditions was also observed for the macrolide antibiotics. Nevertheless, all macrolides were readily removable by bank filtration both under oxic and anoxic conditions.

Behaviour and redox sensitivity of pharmaceutical residues during bank filtration - Investigation of residues of phenazone-type analgesics.

The behaviour of residues of phenazone-type pharmaceuticals during bank filtration was investigated at a field site in Berlin, Germany, where bank-filtered water is used for drinking water production. The concentrations of the pharmaceutical residues in the shallow, young bank filtrate (travel times

Behaviour and biodegradation of sulfonamides (p-TSA, o-TSA, BSA) during drinking water treatment.

Three sulfonamides -para-toluenesulfonamide (p-TSA), ortho-toluenesulfonamide (o-TSA) and benzenesulfonamide (BSA) - have recently been detected in groundwater within a catchment area of one drinking water treatment plant (DWTP), which is located downstream of a former sewage farm. The degradation pathways of p-TSA, o-TSA and BSA were investigated during drinking water treatment with incubation experiments and an experimental filter. Incubation experiments showed that p-TSA is removed during the treatment by microbiological processes. Removal of p-TSA is performed by adapted microorganisms only present in polluted groundwater. The elimination in an experimental filter of 1.6m length applying filtration velocities from 2 to 6 m h(-1) was approximately 93% of p-TSA. The microbial degradation rates in the incubation experiment were approximately 0.029 microg l(-1) h(-1) (zero order reaction). In the experimental filter, the reaction rate constants were around 0.0063 s(-1) for all filtration velocities (1st order reaction). Drinking water treatment does not reduce the concentration of o-TSA and BSA under conditions encountered in Berlin. p-TSA, o-TSA and BSA were only measured in the low microg l(-1) concentrations range in the purified water.

Identification and significance of sulphonamides (p-TSA, o-TSA, BSA) in an urban water cycle (Berlin, Germany).

Because of the nature of the water cycle in Berlin, a number of persistent wastewater residues are present in the surface water and may potentially reach the groundwater via bank filtration and artificial recharge. The occurrence and behaviour of the wastewater residues para-toluenesulphonamide (p-TSA), ortho-toluenesulphonamide (o-TSA) and benzenesulphonamide (BSA) through wastewater treatment, surface water, bank filtration and drinking water treatment was studied. In addition, groundwater below a former sewage farm was investigated. All three compounds are ubiquitous in the aquatic environment of Berlin. p-TSA concentrations are much higher than those of o-TSA and BSA. p-TSA was found in high concentrations in the wastewater influent (2 to 15microg/L), in the wastewater effluent (<0.15 to 2.34microg/L) and in sewage farm groundwater (<0.05 to 20microg/L) and in lower concentrations in the surface water (<0.05 to 1.15microg/L), bank filtrate (<0.05 to 0.30microg/L) and drinking water (<0.05 to 0.54microg/L). p-TSA is considerably depleted during waste- and drinking water treatment ( approximately 90% reduction each). The concentration ranges for o-TSA and BSA in wastewater influents were 0.11 to 8microg/L and <0.05 to 0.64microg/L, respectively, while the values for wastewater effluents were 0.14 to 4microg/L for o-TSA and 0.25 to 0.49microg/L for BSA. Wastewater treatment and drinking water treatment do not reduce the concentrations of o-TSA and BSA. The behaviour of o-TSA during wastewater treatment varies largely between different wastewater treatment plants where concentrations increase, remain constant or decrease. BSA forms during treatment. The concentrations measured in surface water, sewage farm groundwater, bank filtrate and drinking water were <0.05 to 1.74microg/L for o-TSA and <0.05 to 0.53microg/L for BSA.

Quantitative determination of three sulfonamides in environmental water samples using liquid chromatography coupled to electrospray tandem mass spectrometry.

An analytical method was developed to detect the three sulfonamides para-toluenesulfonamide (p-TSA), ortho-toluenesulfonamide (o-TSA) and benzenesulfonamide (BSA) in environmental water samples at concentrations down to 0.02 microg/L using liquid chromatography coupled to tandem mass spectrometry (HPLC-MS/MS). Wastewater, surface water, groundwater and drinking water samples from Berlin (Germany) were analysed for all three compounds which appear to be ubiquitously present in the aquatic environment. p-TSA was found in high concentrations in the wastewater (<0.02-50.8 microg/L) and in groundwater below a former sewage farm (<0.02-41 microg/L), and in lower concentrations in the surface water (<0.02 to 1.15 microg/L) and drinking water (<0.02-0.27 microg/L). o-TSA and BSA were detected in considerably lower concentrations. The study makes clear that p-TSA should be monitored because of its comparatively high concentration in Berlin's drinking water.

Detection and identification of phenazone-type drugs and their microbial metabolites in ground and drinking water applying solid-phase extraction and gas chromatography with mass spectrometric detection.

A new analytical method applying in situ derivatization was developed to enable the extraction of polar drug metabolites from water samples by solid-phase extraction (SPE). An additional derivatization by silylation was used to enhance the sensitivity of analyte detection by gas chromatography-mass spectrometry (GC-MS). Thus, the two metabolites 1,5-di-methyl-1,2-dehydro-3-pyrazolone (DP) and 4-(2-methylethyl)-1,5-dimethyl-1,2-dehydro-3-pyrazolone (PDP), postulated for the degradation of phenazone and propyphenazone, were identified and detected up to the microg/L level in raw and drinking water samples from public water supply.

Identification and significance of phenazone drugs and their metabolites in ground- and drinking water.

Residues of three phenazone-type pharmaceuticals have been identified in routine analyses of groundwater samples from selected areas in the north-western districts of Berlin, Germany. Phenazone, propiphenazone, and dimethylaminophenazone have been detected in some wells at concentrations up to the low microg/l-level. Additionally, three phenazone-type metabolites namely 1-acetyl-1-methyl-2-dimethyl-oxamoyl-2-phenylhydrazide (AMDOPH), 1-acetyl-1-methyl-2-phenylhydrazide, and dimethyloxalamide acid-(N'-methyl-N-phenyl)-hydrazide have also been identified in these groundwater samples. The residues are suspected to originate from former production spills of a pharmaceutical plant located in a city north of Berlin. It was observed that with the exception of AMDOPH all other residues were efficiently removed during conventional drinking water treatment. The drug metabolite AMDOPH deriving from dimethylaminophenazone residues was found at concentrations of 0.9 microg/l in finished drinking water. However, a following study on the toxicological relevance of the AMDOPH residues has shown that there is no toxicological harm for humans at the low concentrations of AMDOPH observed in Berlin drinking water.