N2 yields from monochloramine conversion by granular activated carbons are decisive for effective swimming pool water treatment.

Inorganic chloramines (mono-, di- and trichloramine) are formed in swimming pool water from the unintended reaction of free chlorine with ammonia that is introduced by bathers. Monochloramine is of particular interest as it is known to react further in pool water forming harmful DBPs, such carcinogenic N-nitrosodimethylamine (NDMA). During pool water treatment with granular activated carbon (GAC) filters, monochloramine is transformed by chemical reactions on the carbon surface to N2 and ammonia. As ammonia is led back into the pool where it is chlorinated again under the renewed formation of inorganic chloramines, it is recommended to use GACs with a high N2 yield for monochloramine transformation in pool water treatment. In this study, yields of N2 and ammonia from monochloramine conversion by commercially available GACs were determined using a fixed-bed reactor system under conditions that are typical for swimming pool water treatment. The N2 yields remained constant with on-going exposure of the GAC to monochloramine and ranged from 0.5% to 21.3%, depending on the type of GAC used. Correlation analyses were conducted to identify carbon properties that can determine the N2 yield for monochloramine conversion, such as the amount of oxygen groups, the elemental composition and the trace metal content. It was found that the N2 yield significantly correlates with the copper content of the tested carbons. Model calculations combining pool hydraulics with formation/abatement of inorganic chloramines and NDMA as well as chloramine transformations in GAC filters showed that the concentration of inorganic chloramines and carcinogenic NDMA can be decreased by a factor of ∼2, if the tested GACs could be modified to convert up to ∼50% of the monochloramine to N2.

Portable Analyzer for On-Site Determination of Dissolved Organic Carbon-Development and Field Testing.

Dissolved organic carbon (DOC) is a sum parameter that is frequently used in water analytics. Highly resolved and accurate DOC data are necessary, for instance, for water quality monitoring and for the evaluation of the efficiency of treatment processes. The conventional DOC determination methods consist of on-site sampling and subsequent analysis in a stationary device in a laboratory. However, especially in regions where no or only poorly equipped laboratories are available, this method bears the risk of getting erroneous results. For this reason, the objective of the present study was to set up a reliable and portable DOC analyzer for on-site analysis. The presented DOC system is equipped with an electrolysis-based decomposition cell with boron-doped diamond electrodes (BDD) that oxidizes the organic compounds to carbon dioxide. Within this study, the influence of different electrode materials and the composition of the applied electrolytes on the DOC decomposition in an undivided electrolytic cell were systematically investigated. Furthermore, some technical aspects of the portable prototype are discussed. After a detailed validation, the prototype was used in an ongoing monitoring program in Northern India. The limit of detection is 0.1 mg L-1 C with a relative standard deviation of 2.3% in a linear range up to 1000 mg L C-1. The key features of the portable DOC analyzer are: No need for ultra-pure gases, catalysts or burning technology, an analyzing time per sample below 5 min, and a reliable on-site DOC determination.

Simulating Effluent Organic Matter Competition in Micropollutant Adsorption onto Activated Carbon Using a Surrogate Competitor.

Adsorption onto activated carbon is a promising option for removing organic micropollutants (OMPs) from wastewater treatment plant (WWTP) effluents. The heterogeneity of activated carbons and adsorption competition between OMPs and adsorbable compounds of the effluent organic matter (EfOM) complicate the prediction of OMP removals. Thus, reliable and simple test systems are desirable. For this study, batch experiments with powdered activated carbon (PAC) were carried out to examine methyl orange (MO) as a selected surrogate competitor to simulate EfOM adsorption competition. MO solutions were spiked with carbamazepine (CBZ) as an indicator substance for well-adsorbing OMPs. On the basis of CBZ adsorption isotherms in WWTP effluents, MO concentrations for batch test solutions with identical adsorption competition toward CBZ were calculated. The calculations were performed according to an empirical model of CBZ adsorption in the presence of MO, since predictions employing the ideal adsorbed solution theory (IAST) proved to be inaccurate. Comparative batch tests with five different PACs were conducted with WWTP effluent and respective MO batch test solutions. Except for one PAC, the achieved CBZ removals were very similar in WWTP effluent and the test solution. Additionally, a universal correlation between MO and CBZ removals was found for four PACs.

Sorption of cationic organic substances onto synthetic oxides: Evaluation of sorbent parameters as possible predictors.

Knowledge on the sorption behavior of cationic organic substances in aquatic systems is vital for their risk assessment due to the increasing detection of such chemicals in the hydrosphere. Their sorption behavior is strongly influenced by sorption processes onto mineral surfaces (e.g., oxides, clays). To contribute to the development of prediction tools, the impact of sorbent characteristics on the sorption strength was studied in a highly-idealized model system. In addition to the properties of the solid phase, the concentration of other ions in direct competition for sorption sites and the molecular structure of the sorbate were changed to separate ion exchange and non-ion exchange processes. The study includes in total 120 systematic column experiments using five extensively characterized synthetic oxides (three silica gels, two aluminum oxides), three probe molecules (two structurally related cationic substances, one neutral compound), and four distinctively different NaCl concentrations. The results show that the concentration of OH groups on the sorbent surface is a meaningful descriptor for the observed variations in sorption capacity onto different oxides. Compound-specific linear correlations were obtained, enabling the prediction of sorption coefficients. In addition, a more complex sorption behavior of organic cations compared to uncharged molecules were observed as demonstrated by the sorption results at different electrolyte concentrations. Thus, the study provides an important step towards a better principal mechanistic understanding of organic cation sorption. However, further work using other sorbents including natural ones and other probe molecules is needed to verify the identified relationships within the scope of developing reliable prediction models for cation sorption.

Pore diffusion limits removal of monochloramine in treatment of swimming pool water using granular activated carbon.

Overall apparent reaction rates for the removal of monochloramine (MCA) in granular activated carbon (GAC) beds were determined using a fixed-bed reactor system and under conditions typical for swimming pool water treatment. Reaction rates dropped and quasi-stationary conditions were reached quickly. Diffusional mass transport in the pores was shown to be limiting the overall reaction rate. This was reflected consistently in the Thiele modulus, in the effect of temperature, pore size distribution and of grain size on the reaction rates. Pores <2.5 times the diameter of the monochloramine molecule were shown to be barely accessible for the monochloramine conversion reaction. GACs with a significant proportion of large mesopores were found to have the highest overall reactivity for monochloramine removal.

Production of a bisdemethylated microcystin variant by Planktothrix rubescens.

Reservoir samples from a bloom of Planktothrix rubescens were analyzed by ELISA and LC-MS/MS. The comparison of the results of both methods points to the presence of a microcystin variant not yet available as analytical standard and therefore, not detectable by LC-MS/MS analysis. It is proposed that the unknown cyanotoxin variant is a bisdemethylated microcystin variant, presumably [Asp3,Dha7]-microcystin-RR. [Asp3,Dha7]-MC-RR has not been described for a bloom of P. rubescens before.

Sorption of organic cations onto silica surfaces over a wide concentration range of competing electrolytes.

The fundamental understanding of organic cation-solid phase interactions is essential for improved predictions of the transport and ultimate environmental fates of widely used substances (e.g., pharmaceutical compounds) in the aquatic environment. We report sorption experiments of two cationic model compounds using two silica gels and a natural aquifer sediment. The sorbents were extensively characterized and the results of surface titrations under various background electrolyte concentrations were discussed. The salt dependency of sorption was systematically studied in batch experiments over a wide concentration range (five orders of magnitude) of inorganic ions in order to examine the influence of increasing competition on the sorption of organic cations. The organic cation uptake followed the Freundlich isotherm model and the sorption capacity decreases with an increase in the electrolyte concentration due to the underlying cation exchange processes. However, the sorption recovers considerably at high ionic strength (I>1M). To our knowledge, this effect has not been observed before and appears to be independent from the sorbent characteristics and sorbate structure. Furthermore, the recovery of sorption was attributed to specific, non-ionic interactions and a connection between the sorption coefficient and activity coefficient of the medium is presumed. Eventually, the reasons for the differing sorption affinities of both sorbates are discussed.

Occurrence and Spatial Distribution of Microplastics in River Shore Sediments of the Rhine-Main Area in Germany.

Plastic debris is one of the most significant organic pollutants in the aquatic environment. Because of properties such as buoyancy and extreme durability, synthetic polymers are present in rivers, lakes, and oceans and accumulate in sediments all over the world. However, freshwater sediments have attracted less attention than the investigation of sediments in marine ecosystems. For this reason, river shore sediments of the rivers Rhine and Main in the Rhine-Main area in Germany were analyzed. The sample locations comprised shore sediment of a large European river (Rhine) and a river characterized by industrial influence (Main) in areas with varying population sizes as well as sites in proximity to nature reserves. All sediments analyzed contained microplastic particles (<5 mm) with mass fractions of up to 1 g kg⁻¹ or 4000 particles kg⁻¹. Analysis of the plastics by infrared spectroscopy showed a large abundance of polyethylene, polypropylene, and polystyrene, which covered more than 75% of all polymer types identified in the sediment. Short distance transport of plastic particles from the tributary to the main stream could be confirmed by the identification of pellets, which were separated from shore sediment samples of both rivers. This systematic study shows the emerging pollution of inland river sediments with microplastics and, as a consequence thereof, underlines the importance of rivers as vectors of transport of microplastics into the ocean.

Novel regeneration method for phosphate loaded granular ferric (hydr)oxide--a contribution to phosphorus recycling.

At a progressive rate, small wastewater treatment plants in rural areas need to be equipped with an additional phosphorus removal stage in order to achieve a good chemical status in the receiving natural water bodies. A conventional regeneration method for ferric (hydr)oxides such as phosphate specific adsorbents, which can be applied to remove and recover phosphorus in fixed bed filters, was investigated and improved. It was shown that a loss of up to 85% of the initial capacity can be observed when regeneration with 1 M NaOH is implemented. The losses are caused by surface blocking with different calcium-containing compounds as revealed by an EDX analysis. These blocking compounds could be removed completely with an additional acidic regeneration step at pH = 2.5. During the alkaline desorption that followed, complete phosphorus removal and a full recovery of the adsorption capacity were achieved for goethite-rich Bayoxide(®) E 33 HC (E33HC) and akaganéite-rich GEH(®) 104 (GEH). The regeneration procedure was repeated up to eight times without any signs of further decline in the phosphate adsorption capacity or any changes in the specific surface area or pore size distribution of the adsorbent. In contrast to GEH and E33HC, ferric hydroxide- and calcite-rich FerroSorp(®) Plus (FSP) was partly dissolved during acid treatment.

Impact of EfOM size on competition in activated carbon adsorption of organic micro-pollutants from treated wastewater.

The competitive impacts of different fractions of wastewater treatment plant effluent organic matter (EfOM) on organic micro-pollutant (OMP) adsorption were investigated. The fractionation was accomplished using separation by nanofiltration (NF). The waters resulting from NF were additionally treated to obtain the same dissolved organic carbon (DOC) concentrations as the initial water. Using size exclusion chromatography (LC-OCD) it could be shown that the NF treatment resulted in an EfOM separation by size. Adsorption tests showed different competitive effects of the EfOM fractions with the OMP. While large EfOM compounds that were retained in NF demonstrated a reduced competition as compared to the raw water, the NF-permeating EfOM compounds showed an increased competition with the majority of the measured OMP. The effects of small size EfOM are particularly negative for OMP which are weak/moderate adsorbates. Adsorption analysis was carried out for the differently fractionized waters. The small sized EfOM contain better adsorbable compounds than the raw water while the large EfOM are less adsorbable. This explains the observed differences in the EfOM competitiveness. The equivalent background compound (EBC) model was applied to model competitive adsorption between OMP and EfOM and showed that the negative impacts of EfOM on OMP adsorption increase with decreasing size of the EfOM fractions. The results suggest that direct competition for adsorption sites on the internal surface of the activated carbon is more substantial than indirect competition due to pore access restriction by blockage. Another explication for reduced competition by large EfOM compounds could be the inability to enter and block the pores due to size exclusion.

Sorption of the organic cation metoprolol on silica gel from its aqueous solution considering the competition of inorganic cations.

Systematic batch experiments with the organic monovalent cation metoprolol as sorbate and the synthetic material silica gel as sorbent were conducted with the aim of characterizing the sorption of organic cations onto charged surfaces. Sorption isotherms for metoprolol (>99% protonated in the tested pH of around 6) in competition with mono- and divalent inorganic cations (Na(+), NH4(+), Ca(2+), and Mg(2+)) were determined in order to assess their influence on cation exchange processes and to identify the role of further sorptive interactions. The obtained sorption isotherms could be described well by an exponential function (Freundlich isotherm model) with consistent exponents (about 0.8). In general, a decreasing sorption of metoprolol with increasing concentrations in inorganic cations was observed. Competing ions of the same valence showed similar effects. A significant sorption affinity of metoprolol with ion type dependent Freundlich coefficients KF,0.77 between 234.42 and 426.58 (L/kg)(0.77) could still be observed even at very high concentrations of competing inorganic cations. Additional column experiments confirm this behavior, which suggests the existence of further relevant interactions beside cation exchange. In subsequent batch experiments, the influence of mixtures with more than one competing ion and the effect of a reduced negative surface charge at a pH below the point of zero charge (pHPZC ≈ 2.5) were also investigated. Finally, the study demonstrates that cation exchange is the most relevant but not the sole mechanism for the sorption of metoprolol on silica gel.

Vacuum-UV radiation at 185 nm in water treatment--a review.

The vacuum-UV radiation of water results in the in situ generation of hydroxyl radicals. Low-pressure mercury vapor lamps which emit at 185 nm are potential sources of VUV radiation. The scope of this article is to give an overview of the application of VUV radiation at 185 nm for water treatment including the transformation of inorganic and organic water constituents, and the disinfection efficiency. Another focus is on the generation of ozone by VUV radiation from oxygen or air and the application of the produced ozone in combination with VUV irradiation of water in the VUV/O3 process. The advantages and limitation of the VUV process at 185 nm as well as possible applications in water treatment are outlined.

Disinfection of biologically treated wastewater and prevention of biofouling by UV/electrolysis hybrid technology: influence factors and limits for domestic wastewater reuse.

Reuse of wastewater contributes significantly to an efficient and sustainable water usage. However, due to the presence of a multitude of pathogens (e.g. bacteria, viruses, worms, protozoa) in secondary effluents, disinfection procedures are indispensable. In decentralized wastewater treatment, UV irradiation represents one of the most common disinfection methods in addition to membrane processes and to a certain extent electrochemical procedures. However, the usage of UV disinfected secondary effluents for domestic (sanitary) or irrigation purposes bears a potential health risk due to the possible photo and dark repair of reversibly damaged bacteria. Against this background, the application of the UV/electrolysis hybrid technology for disinfection and prevention of bacterial reactivation in biologically treated wastewater was investigated in view of relevant influence factors and operating limits. Furthermore, the influence of electrochemically generated total oxidants on the formation of biofilms on quartz glass surfaces was examined, since its preventive avoidance contributes to an enhanced operational safety of the hybrid reactor. It was found that reactivation of bacteria in UV irradiated, biologically treated wastewater can be prevented by electrochemically produced total oxidants. In this regard, the influence of the initial concentration of the microbiological indicator organism Escherichia coli (E. coli) (9.3*10(2)-2.2*10(5) per 100 mL) and the influence of total suspended solids (TSS) in the range of 11-75 mg L(-1) was examined. The concentration of total oxidants necessary for prevention of bacterial regrowth increases linearly with the initial E. coli and TSS concentration. At an initial concentration of 933 E. coli per 100 mL, a total oxidants concentration of 0.4 mg L(-1) is necessary to avoid photo reactivation (at 4200 Lux), whereas 0.67 mg L(-1) is required if the E. coli concentration is enhanced by 2.4 log levels (cTSS = constant = 13 mg L(-1)). The prevention of dark repair is ensured with 25-50% lower concentration of total oxidants. An increase of the TSS concentration from 11 mg L(-1) to 75 mg L(-1) leads to a triplication of the need of total oxidants from 0.6 mg L(-1) to 1.8 mg L(-1) (3*10(5)E. coli per 100 mL). The energy consumption of the hybrid reactor varies from 0.17 kWh m(-3) to 0.94 kWh m(-3) depending on the TSS concentration (11-75 mg L(-1)). Furthermore, biofilm formation on quartz glass surfaces, of which the sleeves of UV lamps consist, can be suppressed by electrochemically produced total oxidants at a concentration of at least 1 mg L(-1) which ensures high operational safety of the hybrid reactor combined with large maintenance intervals.

Homologue specific analysis of a polyether trisiloxane surfactant in German surface waters and study on its hydrolysis.

The occurrence of a polyether trisiloxane surfactant in the ng L(-1) range in German surface waters is reported for the first time. The studied surfactant does not ubiquitously occur in the aquatic environment but can reach surface waters on a local scale. As a first step towards the understanding of the environmental fate, the hydrolysis was studied according to the OECD guideline 111. It confirmed that the trisiloxane surfactant is sensitive to hydrolysis and that the hydrolysis rate strongly depends on the pH and the temperature. If one takes only into account the hydrolysis, the trisiloxane surfactant could persist several weeks in river water (the half-life in water is approximately 50 days at pH 7, 25 °C, and an initial concentration of 2 mg L(-1)). A degradation product, more polar than the initial trisiloxane surfactant, was identified by high resolution mass spectrometry.

Investigation of uranium binding forms in selected German mineral waters.

Cryogenic time-resolved laser-induced fluorescence spectroscopy was successfully used to identify uranium binding forms in selected German mineral waters of extremely low uranium concentrations (<2.0 µg/L). The measurements were performed at a low temperature of 153 K. The spectroscopic data showed a prevalence of aquatic species Ca2UO2(CO3)3 in all investigated waters, while other uranyl-carbonate complexes, viz, UO2CO3(aq) and UO2(CO3)2 (2-), only existed as minor species. The pH value, alkalinity (CO3 (2-)), and the main water inorganic constituents, specifically the Ca(2+) concentration, showed a clear influence on uranium speciation. Speciation modeling was performed using the most recent thermodynamic data for aqueous complexes of uranium. The modeling results for the main uranium binding form in the investigated waters indicated a good agreement with the spectroscopy measurements.

Determination of adsorbable organic fluorine from aqueous environmental samples by adsorption to polystyrene-divinylbenzene based activated carbon and combustion ion chromatography.

A new method for the determination of trace levels of adsorbable organic fluorine (AOF) in water is presented. Even if the individual contributing target compounds are widely unknown, this surrogate parameter is suited to identify typical organofluorine contaminations, such as with polyfluorinated chemicals (PFCs), and represents a lower boundary of the organofluorine concentration in water bodies. It consists of the adsorption of organofluorine chemicals on a commercially available synthetic polystyrene-divinylbenzene based activated carbon (AC) followed by analysis of the loaded AC by hydropyrolysis combustion ion chromatography (CIC). Inorganic fluorine is displaced by excess nitrate during the extraction step and by washing the loaded activated carbon with an acidic sodium nitrate solution. Due to its high purity the synthetic AC had a very low and reproducible fluorine blank (0.3 µg/g) compared to natural ACs (up to approximately 9 µg/g). Using this AC, fluoride and the internal standard phosphate could be detected free of chromatographic interferences. With a sample volume of 100 mL and 2× 100 mg of AC packed into two extraction columns combined in series, a limit of quantification (LOQ), derived according to the German standard method DIN 32645, of 0.3 µg/L was achieved. The recoveries of six model PFCs were determined from tap water and a municipal wastewater treatment plant (WWTP) effluent. Except for the extremely polar perfluoroacetic acid (recovery of approximately 10%) the model substances showed fairly good (50% for perfluorobutanoic acid (PFBA)) to very good fluorine recoveries (100±20% for perfluorooctanoic acid (PFOA), perfluorobutanesulfonate (PFBS), 6:2 fluorotelomersulfonate (6:2 FTS)), both from tap water and wastewater matrix. This new analytical protocol was exemplarily applied to several surface water and groundwater samples. The obtained AOF values were compared to the fluorine content of 19 target PFCs analyzed by high performance liquid chromatography-electrospray tandem mass spectrometry (HPLC-(-)ESI-MS/MS). In groundwater contaminated by PFC-containing aqueous film-forming foams (AFFFs) up to 50% of the AOF could be attributed to PFC target chemicals, while in diffuse contaminated samples only <5% of the AOF could be identified by PFC analysis.

Influence of competing inorganic cations on the ion exchange equilibrium of the monovalent organic cation metoprolol on natural sediment.

The aim of this study was to systematically investigate the influence of the mono- and divalent inorganic ions Na(+) and Ca(2+) on the sorption behavior of the monovalent organic cation metoprolol on a natural sandy sediment at pH=7. Isotherms for the beta-blocker metoprolol were obtained by sediment-water batch tests over a wide concentration range (1-100000 µg L(-1)). Concentrations of the competing inorganic ions were varied within freshwater relevant ranges. Data fitted well with the Freundlich sorption model and resulted in very similar Freundlich exponents (n=0.9), indicating slightly non-linear behavior. Results show that the influence of Ca(2+) compared to Na(+) is more pronounced. A logarithmic correlation between the Freundlich coefficient K(Fr) and the concentration or activity of the competing inorganic ions was found allowing the prediction of metoprolol sorption on the investigated sediment at different electrolyte concentrations. Additionally, the organic carbon of the sediment was completely removed for investigating the influence of organic matter on the sorption of metoprolol. The comparison between the experiments with and without organic carbon removal revealed no significant contribution of the organic carbon fraction (0.1%) to the sorption of metoprolol on the in this study investigated sediment. Results of this study will contribute to the development of predictive models for the transport of organic cations in the subsurface.

Role of cation exchange processes on the sorption influenced transport of cationic ß-blockers in aquifer sediments.

The influence of cation exchange processes on the transport behavior of the cationic ß-blockers atenolol and metoprolol was investigated by applying saturated laboratory column experiments. Breakthrough curves using natural sediments under different competitive conditions were generated and resulting sorption coefficients were compared. For the cationic species of atenolol (at pH = 8), the existence and dominating role of cation exchange processes were demonstrated by varying calcium concentrations. No effect of atenolol concentration on its retardation was observed within a wide concentration range. The breakthrough curve comparison of atenolol and the more hydrophobic metoprolol under constant conditions showed a significantly stronger retardation for metoprolol than for atenolol. However, additional non-polar interactions cannot explain the observed differences as they are determined to be negligible for both compounds. Due to the dominating role of cation exchange processes for the cationic species on overall sorption, a simple prediction of ß-blocker transport in the subsurface by using K(OC) values derived from log K(OW)-log K(OC) correlations is not feasible.

UV-based advanced oxidation processes for the treatment of odour compounds: efficiency and by-product formation.

The occurrence of the taste and odour compounds geosmin and 2-methyl isoborneol (2-MIB) affects the organoleptic quality of raw waters from drinking water reservoirs worldwide. UV-based oxidation processes for the removal of these substances are an alternative to adsorption and biological processes, since they additionally provide disinfection of the raw water. We could show that the concentration of geosmin and 2-MIB could be reduced by VUV irradiation and the combination of UV irradiation with ozone and hydrogen peroxide in pure water and water from a drinking water reservoir. The figure of merit EE/O is an appropriate tool to compare the AOPs and showed that VUV and UV/O(3) yielded the lowest treatment costs for the odour compounds in pure and raw water, respectively. Additionally, VUV irradiation with addition of ozone, generated by the VUV lamp, was evaluated. The generation of ozone and the irradiation were performed in a single reactor system using the same low-pressure mercury lamp, thereby reducing the energy consumption of the treatment process. The formation of the undesired by-products nitrite and bromate was investigated. The combination of VUV irradiation with ozone produced by a VUV lamp avoided the formation of relevant concentrations of the by-products. The internal generation of ozone is capable to produce ozone concentrations sufficient to reduce EE/O below 1 kWh m(-3) and without the risk of the formation of nitrite or bromate above the maximum contaminant level.

Development of a liquid chromatography tandem mass spectrometry method for trace analysis of trisiloxane surfactants in the aqueous environment: an alternative strategy for quantification of ethoxylated surfactants.

Trisiloxane surfactants, often referred to as superspreaders or superwetters, are added to pesticides to enhance the activity and the rainfastness of the active substance by promoting rapid spreading over hydrophobic surfaces. To fill the lack of data on the environmental occurrence of these compounds, we have developed and validated a method for their trace analysis in the aqueous environment. The method is based on liquid-liquid extraction followed by liquid chromatography and tandem mass spectrometry. The oligomeric distribution of trisiloxane surfactant in a reference solution was determined by a theoretical calculation and by experimental measurements. Based on these results, the quantification was performed by comparison with a calibration made with a single homologue instead of a mixture of homologues. This approach avoids a time-consuming synthesis of pure homologues and reduces the risk of wrong estimation of the concentration because of different response factors of the sample and the standard. Such an approach could be applied to the quantification of other ethoxylated surfactants following a similar distribution. The validation was performed from 2 to 250 ng/L (total surfactant concentration) in deionized water, tap water, and river water (Rhine water). Knowing the oligomeric distribution of the polymer in the reference solution, the corresponding calibration ranges were estimated for individual homologues. Limits of quantification were found to be between 0.37 ng/L and 15 ng/L. The total recovery of sample preparation was between 77% and 116%. Matrix effects were lower than 10% with river water and the relative standard deviation evaluated over ten identical samples of spiked river water was below 12%.