Trace analysis of benzophenone-type UV filters in water and their effects on human estrogen and androgen receptors.

To carry out risk assessments of benzophenone-type UV filters (BPs), fast and accurate analytical methods are crucial to determine and monitor levels in the environment. This study presents an LC-MS/MS method that requires minimal sample preparation and yet can identify 10 different BPs in environmental samples such as surface or wastewater resulting in a LOQ range from 2 to 1060 ng/L. The method suitability was tested through environmental monitoring, which showed that, BP-4 is the most abundant derivative found in the surface waters of Germany, India, South Africa and Vietnam. BP-4 levels correlate with the WWTP effluent fraction of the respective river for selected samples in Germany. Peak values of 171 ng/L for 4-hydroxybenzophenone (4-OH-BP), as measured in Vietnamese surface water, already exceed the PNEC value of 80 ng/L, elevating 4-OH-BP to the status of a new pollutant that needs more frequent monitoring. Moreover, this study reveals that during biodegradation of benzophenone in river water, the transformation product 4-OH-BP is formed which contain structural alerts for estrogenic activity. By using yeast-based reporter gene assays, this study provides bio-equivalents of 9 BPs, 4-OH-BP, 2,3,4-tri-OH-BP, 4-cresol and benzoate and complements the existing structure-activities relationships of BPs and their degradation products.

Natural Zeolites for the Sorption of Ammonium: Breakthrough Curve Evaluation and Modeling.

The excessive use of ammonium fertilizer and its associated leakage threatens aquatic environments around the world. With a focus on the treatment of drinking water, the scope of this study was to evaluate and model the breakthrough curves for NH4+ in zeolite-filled, fixed-bed columns. Breakthrough experiments were performed in single- and multi-sorbate systems with the initial K+ and NH4+ concentrations set to 0.7 mmol/L. Breakthrough curves were successfully modeled by applying the linear driving force (LDF) and Thomas models. Batch experiments revealed that a good description of NH4+ sorption was provided by the Freundlich sorption model (R2 = 0.99), while unfavorable sorption was determined for K+ (nF = 2.19). Intraparticle diffusion was identified as the rate limiting step for NH4+ and K+ during breakthrough. Compared to ultrapure water, the use of tap, river, and groundwater matrices decreased the treated bed volumes by between 25% and 69%-as measured at a NH4+ breakthrough level of 50%. The concentrations of K+ and of dissolved organic carbon (DOC) were identified as the main parameters that determine NH4+ sorption in zeolite-filled, fixed-bed columns. Based on our results, the LDF and Thomas models are promising tools to predict the breakthrough curves of NH4+ in zeolite-filled, fixed-bed columns.

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.

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.

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.

Electrochemical disinfection of biologically treated wastewater from small treatment systems by using boron-doped diamond (BDD) electrodes--contribution for direct reuse of domestic wastewater.

The aim of the study was to demonstrate the application potential of boron-doped diamond electrodes (BDD) in electrochemical disinfection of biologically treated sewage for direct recycling of domestic wastewater. Discontinuous bulk disinfection experiments with secondary effluents and model solutions were performed to investigate the influence of operating conditions and wastewater parameters on disinfection efficiency and formation of disinfection by-products (adsorbable organically bound halogens, AOX). The inactivation rate accelerates with increasing current density caused by a faster generation of electrochemical oxidants (ECO). It could be shown that the effect of OH radicals in case of the direct electrochemical disinfection of chloride-containing secondary effluents with BDD is negligible because of their fast reaction with typical radical scavengers. The dominating role of electrochemically generated free chlorine in the disinfection process could be explicitly verified. It could be also shown that the disinfection efficiency is strongly affected by the specific wastewater parameters temperature and pH. These effects can be explained by the behaviour of the reactive species. The migration-controlled generation of ECO can be accelerated under turbulent hydrodynamic conditions. The formation of disinfection by-products (AOX) correlates with the introduced electric charge Q applied per volume and is independent of the applied current density.

The effect of water temperature on the adsorption equilibrium of dissolved organic matter and atrazine on granular activated carbon.

The influence of water temperature on the adsorption of natural dissolved organic matter (DOM) on activated carbon has not been investigated intensively yet. In this study, batch experiments with granular activated carbon (GAC) have been carried out at three temperatures (5 degrees C, 20 degrees C, 35 degrees C) using a humic acid model water and different types of surface water (lake, river, canal). Furthermore, the adsorption of an anthropogenic contaminant, atrazine, was quantified in the absence and presence of DOM. The results indicate a significant influence of water temperature on the adsorption equilibrium of DOM and atrazine. Contrary to expectations, DOM and atrazine adsorption in surface water tends to be increased with increasing water temperature, whereas the extent of this effect is dependent on the type and concentration of DOM. Furthermore, the temperature effect on atrazine adsorption is controlled by competition of DOM and atrazine on adsorption sites. Some assumptions are proposed and discussed for explaining the temperature effects observed in the batch studies.

Adsorption of dissolved organic matter onto activated carbon--the influence of temperature, absorption wavelength, and molecular size.

In this study, batch and column adsorption experiments with granular activated carbon (GAC) were carried out for removing dissolved organic matter (DOM) of a pond water at different water temperatures (5, 20, and 35 degrees C). The water was characterized before and after the adsorption step using UV/VIS spectroscopy and size-exclusion chromatography (SEC) combined with diode array detection (DAD). DOM breakthrough of GAC filters has been found to be slower at higher water temperatures, the DOM removal being most effective at 35 degrees C. UV/VIS spectra and SEC chromatograms of water samples treated at different water temperatures indicate that an increase in temperature especially supports the adsorption of small DOM molecules as well as molecules absorbing at higher wavelengths, specifying aromatic structures of DOM. SEC-DAD has been demonstrated to be an efficient method for characterizing DOM of natural waters and for detecting relative changes of DOM during the water treatment process.