IWW Water Centre
  • Biebesheim, Germany
Recent publications
Biogeochemical redox processes control the chemical behavior of many major and trace elements, making their comprehension crucial for predicting and protecting environmental health. Nitrogen is especially susceptible to changes in soil redox conditions and affects the cycles of other redox-sensitive species. Elevated nitrogen concentrations, in nitrate form, in agricultural soils and associated freshwater ecosystems constitute a problem in many parts of the world. Although a wide variety of measures have already been adopted, their assessment through concentration measurements in groundwater and surface water of the different monitoring networks has shortcomings. Nitrate, as a non-point pollutant, is subject to several processes, such as transformation and retardation, before it is detected, making it impossible to evaluate measurements' effectiveness reliably. Thus, we designed and constructed a monitoring station featuring commercially-available products and self-manufactured components at an agricultural site for the in-situ assessment of nitrate-related processes by high-resolution monitoring of hydraulic (soil water content, matric potential, groundwater head) and hydrogeochemical variables (oxidation-reduction potential, ground-, and pore water chemistry) within the vadose zone and the shallow aquifer. The monitoring station has proven to be a reliable tool. Changes over depth and time of measured variables have been identified, allowing the detection of the transient behavior of the redox reactive zone, the interpretation of ongoing denitrification processes, and other redox nitrate-triggered phenomena such as uranium roll-front and selenium accumulation at the redox interface. Measuring both geochemical and soil water variables allows for the calculation of in-situ solute inputs into the groundwater and their reaction rates. This article is protected by copyright. All rights reserved.
Migration of emerging contaminants (ECs) from pipes into water is a global concern due to potential human health effects. Nevertheless, a review of migration ECs from pipes into water distribution systems is presently lacking. This paper reviews, the reported occurrence migration of ECs from pipes into water distribution systems in the world. Furthermore, the results related to ECs migration from pipes into water distribution systems, their probable sources, and their hazards are discussed. The present manuscript considered the existing reports on migration of five main categories of ECs including microplastics (MPs), bisphenol A (BPA), phthalates, nonylphenol (NP), perfluoroalkyl, and polyfluoroalkyl substances (PFAS) from distribution network into tap water. A focus on tap water in published literature suggests that pipes type used had an important role on levels of ECs migration in water during transport and storage of water. For comparison, tap drinking water in contact with polymer pipes had the highest mean concentrations of reviewed contaminants. Polyvinyl chloride (PVC), polyamide (PA), polypropylene (PP), polyethylene (PE), and polyethylene terephthalate (PET) were the most frequently detected types of microplastics (MPs) in tap water. Based on the risk assessment analysis of ECs, levels of perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA), perfluorohexane sulfonate (PFHxS), and perfluorooctane sulfonate (PFOS) were above 1, indicating a potential non-carcinogenic health risk to consumers. Finally, there are still scientific gaps on occurrence and migration of ECs from pipes used in distribution systems, and this needs more in-depth studies to evaluate their exposure hazards on human health.
The upgrading of large informal settlement areas takes place in sections for technical, economic and social reasons. On one hand, planning is faced with the challenge of taking individual structural and social conditions into account when dividing up the districts. On the other hand, the routing of the mains of a pipe-based infrastructure (water supply) must be selected in the context of the entire area under consideration and integrated into a superordinate network layout. In this paper, a method that combines these contrasting approaches is presented. Potential district boundaries are identified based on existing infrastructure and development patterns, as well as considering the routing requirements of a piped drinking water supply. Thereby, social factors can be considered in the decision-making process. Subsequently, an area subdivision is performed by a recursive partitioning algorithm. The choice and combination of different compactness measures influence the shape of the districts and, thus, the spatial organization. The geodetic height is integrated into the algorithm via an admissibility condition, so that the subsequent development of a district can take place via one pressure zone. By means of variations in the input parameters of the zoning, different planning levels can be generated, which finally lead successively to the upgrading of an informal settlement area.
The persistent, mobile and toxic ether 1,4-dioxane poses a risk to German drinking water production. Even though groundwater provides the largest share of German drinking water supply, regionally, these resources have to be complemented by surface waters, which are locally exceeding the German drinking water guidance value of 5 μg/L. Contamination predominantly originates from wastewater treatment plant (WWTP) effluents as major point sources. Case studies show that commonly applied raw water extraction methods such as river bank filtration (RBF) do not act as sufficient barriers against source water contamination with 1,4-dioxane, consequently, drinking water concentrations of up to >2 μg/L were determined. AOPs introduced as emission mitigation measures and assessed against surface and drinking water concentrations resulted in a reduction therein. Since 1,4-dioxane has also been proven to be a contaminant in German groundwater in concentrations of up to 150 μg/L at selected sites, drinking water relevant groundwater should be increasingly monitored.
Ecotoxicological effects of photolytic degradation mixtures of the two brominated flame retardants PolymericFR and Tetrabromobisphenol A-bis (2,3-dibrom-2-methyl-propyl) Ether (TBBPA-BDBMPE) have been studied in vitro and in vivo. Both substances were experimentally degraded separately by exposure to artificial UV-light and the resulting degradation mixtures from different time points during the UV-exposure were applied in ecotoxicological tests. The in vitro investigation showed no effects of the degraded flame retardants on the estrogenic and androgenic receptors via the CALUX (chemically activated luciferase gene expression) assay. Short-term exposures (up to 96 h) of Lumbriculus variegatus lead to temporary physiological reactions of the annelid. The exposure to degraded PolymericFR lead to an increased activity of Catalase, while the degradation mixture of TBBPA-BDBMPE caused increases of Glutathione-S-transferase and Acetylcholine esterase activities. Following a chronic exposure (28 d) of L. variegatus, no effects on the growth, reproduction, fragmentation and energy storage of the annelid were detected. The results indicate that the experimental degradation of the two flame retardants causes changes in their ecotoxicological potential. This might lead to acute physiological effects on aquatic annelids, which, however, do not affect the animals chronically according to our results.
In this study, we analyzed the concentration distributions of 20 polycyclic aromatic hydrocarbons (PAHs) in 41 water samples which were collected from the northern part of Taihu Lake during 4 field campaigns (201511, 201606, 201702 and 201709). The concentrations were determined with GC–MS, and their spatial and seasonal distribution characteristics were interpreted. The results show that 2-ring PAHs present considerably higher concentrations in warm seasons than cold seasons, but the concentrations of the other higher-ring PAHs are rather stable in warm and cold seasons. The distribution patterns of these PAHs might be mainly attributed to ambient temperature effects on the PAH solubility in the water body. Meanwhile, the spatial distributions of the PAH concentrations in cold seasons were rather various in the sampling area, while the distributions in the warm seasons were homogeneous. The different distributions could result from the water recharge from the Yangtze River during cold seasons, which diluted PAH concentrations in the northeastern part of the lake. Furthermore, via literature review on PAH concentrations in water body, PAHs are in a wide range of levels and their patterns are different among the studies, which should be more effected by local factors instead of general PAH properties. The results from this study also present special characteristics of PAHs in Taihu Lake, which exhibit more insight on PAHs existence in water bodies.
The analysis of fatty acid methyl esters (FAMEs) is of high relevance for monitoring and control of various industrial processes and biological systems. In this study, a novel, green analytical approach for the determination of 24 FAMEs from aqueous samples is proposed, which is based on a headspace solid-phase microextraction (SPME) arrow followed by gas chromatography coupled to tandem mass spectrometry (GC–MS/MS). The method was substantially accelerated to a run time of 44 min per sample by thorough optimization and automation of the relevant parameters. The limiting parameters, mostly based on expediting equilibrium attainment, were found to be parameters of extraction: material, pH, time, and temperature, which were optimized to divinylbenzene polydimethylsiloxane (DVB-PDMS), pH 2, 20 min, and 70 °C, respectively. The optimization and automation of the method led to low method detection limits (9–437 ng L ⁻¹ ) and high selectivity. Evaluation of the method on real samples was done by analyzing the aqueous phase of a bioreactor, whereby the matrix effect could be greatly reduced due to dilution and headspace sampling. The rapid, sensitive, selective, and matrix-reduced approach is found to be not only a novel method for water analysis but is promising for further applications, e.g., with solid and gaseous samples containing FAMEs. Graphical abstract
Due to its ubiquitous presence in wastewaters, wastewater treatment plant effluents and even surface waters, the removal of the pharmaceutical ibuprofen from water is of special interest. Ozonation is widely applied for the treatment of micropollutants in wastewater treatment plants and is already known to also degrade ibuprofen. However, the formation of a wide range of transformation products during such oxidation steps might affect the aquatic environment. This study focuses on the acute ecotoxicological impact of the ibuprofen ozonation products on the two model organisms Daphnia magna and Desmodesmus subspicatus. For the identification of possibly ecotoxic products, a new workflow combining ecotoxicological testing, analytical methods and toxicity prediction was applied. Examination at different pH conditions with increasing ozone doses can point to respective products for further systematic examination. Seven ozonation products were confirmed in this study, two of them for the first time. Five previously postulated products were rejected. For pH 7 the inhibition of green algae growth was observed for mixtures oxidized with low ozone doses, while at pH 3 the mixtures with higher ozone doses caused toxic effects on the mobility of daphnids. Together with the analytical measurements in combination with ecotoxicity prediction, six products were identified which might have caused the toxic effect on green algae. However, no assignment to the observed toxic effects on daphnids was possible. The gained results indicate that mixture toxicity might play a role in oxidation processes and needs to be considered in ozonation studies concerning the ecotoxicological impact. Furthermore, the different observed toxicity for the two organisms underlines the importance of using multiple test systems for a comprehensive evaluation of the ecotoxicity during ozonation processes.
Wastewater treatment plants (WWTPs) may represent point sources for microplastic discharge into the environment. Quantification of microplastic in effluents of WWTPs has been targeted by several studies although standardized methods are missing to enable a comparability of results. This study discusses theoretical and practical perspectives on best practices for microplastic sampling campaigns of WWTPs. One focus of the study was the potential for synergies between thermoanalytical and spectroscopic analysis to gain more representative sampling using the complementary information provided by the different analytical techniques. Samples were obtained before and after sand filtration from two WWTPs in Germany using cascade filtration with size classes of 5,000 – 100 µm, 100 – 50 µm, and 50 – 10 µm. For spectroscopic methods samples were treated by a Fenton process to remove natural organic matter, whereas TED-GC-MS required only sample extraction from the filter cascade. µFTIR spectroscopy was used for the 100 µm and 50 µm basket filters and µRaman spectroscopy was applied to analyze particles on the smallest basket filter (10 µm). TED-GC-MS was used for all size classes as it is size independent. All techniques showed a similar trend, where PE was consistently the most prominent polymer in WWTP effluents. Based on this insight, PE was chosen as surrogate polymer to investigate whether it can describe the total polymer removal efficiency of tertiary sand filters. The results revealed no significant difference (ANOVA) between retention efficiencies of tertiary sand filtration obtained using only PE and by analyzing all possible polymers with µFTIR and µRaman spectroscopy. Findings from this study provide valuable insights on advantages and limitations of cascade filtration, the benefit of complementary analyses, a suitable design for future experimental approaches, and recommendations for future investigations.
A continuously operating system for monitoring groundwater contamination by aromatic VOCs has been developed. For this purpose, a novel gas-water separation unit was to be used in combination with APPI-FAIMS. The gas-water separation unit successfully reduced the humidity in the sample flow to ≤1.6 ppmv prior to analyte ionization. Initially, toluene was selected as a model aromatic VOC. The quantitative response of toluene, as a single VOC in water (LOD <1 mg L⁻¹), was used to investigate the feasibility of the monitoring system and the effect of humidity on the signal produced by the APPI-FAIMS. With humidity increase (up to 400 ppmv) an increase of the toluene signal for about 30% was observed, including the possible formation and detection of water clusters and toluene-water clusters. Similar effects were noted in the case of benzene. However, for the detection of single contaminants such as indane and trimethylbenzenes (TMBs) this was not observed even at relative high humidity (500 ppmv). Additionally, on-site, continuous, groundwater monitoring of the aromatic VOCs contamination was carried out successfully with the gas-water separation APPI-FAIMS at low humidity (0.3–1.6 ppmv) allowing simplified monitoring of a specific, total aromatic VOCs signal in groundwater.
For decades, infrastructure planning in informal settlements has been a major challenge for urban planners and engineers. In particular, the planning process for the rapidly changing heterogeneous structures in these areas usually require individual and non-sustainable solutions. In this report, a method for the sustainable and practical planning of a piped water distribution system (WDS) that generates different expansion variants as a planning support tool is presented. In this tool, all real-world routing options are included in the decision-making process, based on the existing infrastructure, settlement structure, and identifiable open spaces. Additionally, proposals for the localization of the future public water points are supported by methods from Logistics. The consideration of the existing settlement structure and real route lengths (pedestrian walking distance) to a potential water point location lead to very practical and realizable results. The principle of participatory planning was considered, to easily include individual adjustments at any given timeframe. At the same time, automated processes generate fast results. The method is modular and linked to a geographic information system (GIS) to directly visualize the impacts and effects of the planning and decision-making process.
A pilot scale chlorine contact tank (CCT) with flexible baffling was installed at an operational water treatment plant (WTP), taking a direct feed from the outlet of the rapid gravity filters (RGF). For the first time, disinfection efficacy was established by direct microbial monitoring in a continuous reactor using flow cytometry (FCM). Disinfection variables of dose, time, and hydraulic efficiency (short circuiting and dispersion) were explored following characterisation of the reactor's residence time distributions (RTD) by tracer testing. FCM enabled distinction to be made between changes in disinfection reactor design where standard culture-based methods could not. The product of chlorine concentration (C) and residence time (t) correlated well with inactivation of microbes, organisms, with the highest cell reductions (N/N0) reaching <0.025 at Ctx̄ of 20 mg.min/L and above. The influence of reactor geometry on disinfection was best shown from the Ct10. This identified that the initial level of microbial inactivation was higher in unbaffled reactors for low Ct10 values, although the highest levels of inactivation of 0.015 could only be achieved in the baffled reactors, because these conditions enabled the highest Ct10 values to be achieved. Increased levels of disinfection were closely associated with increased formation of the trihalomethane disinfection by-products. The results highlight the importance of well-designed and operated CCT. The improved resolution afforded by FCM provides a tool that can dynamically quantify disinfection processes, enabling options for much better process control.
Denitrification in soils and aquifers sustains low nitrate concentrations in many anaerobic groundwaters despite massive inputs of N from agriculture. However, this ecosystem service sometimes comes at the cost of trace metal mobilization and concerns have been raised that denitrification in anaerobic groundwater may lead to trace metal contamination. But it remains unclear, if denitrification must necessarily result in trace metal concentrations that are potentially harmful for humans. For example, formation of iron(oxy)hydroxides after the reaction of nitrate with pyrite may reduce rather than increase the mobility of certain trace metals in aquifers. We quantified the potential health risk resulting from denitrification-associated trace metal pollution (Mn, Ni, As, Cd, U) in anaerobic groundwater with different degrees of nitrate pollution in >800 wells located in Northern Germany. Overall, observed rates of violations of legal quality standards for U, As and Cd are moderate in the study area (<10% of all wells) but elevated for Mn (>50%), which is a common contaminant under the often anaerobic conditions in the study area. However, in groundwater where denitrification had partially proceeded, the risk for drinking water standard violations was higher for Ni, Cd and U (up to a factor of 4 for Ni) as compared to anaerobic groundwater without denitrification, but lower for Mn and As. Especially poorly buffered groundwaters with pH < 5.5 are at risk of Ni and Cd contamination resulting from denitrification, while the opposite is true for Mn and U. Thus, we establish a clear linkage between nitrogen biogeochemistry and trace metal mobility and show how perturbations of groundwater redox and pH conditions by nitrate can further deteriorate groundwater quality. In addition, we find that the combination of oxygen concentrations of lower than 1 mg L−1, and nitrate concentrations above 1 mg L⁻¹ allows for identification of denitrification (as evidenced by excess N2 in groundwater) with 90% accuracy. The methodology developed herein can be used to inform water treatment planning about potential trace metal contamination when drinking water should be produced from anaerobic aquifers beneath agricultural landscapes.
The prevalence of organic micropollutants (OMPs) in aquatic environment has expedited scientific and regulatory efforts to retrofit existing wastewater treatment plants (WWTPs). The current strategy involves WWTPs upgrading with post-ozonation i.e., ozone (O3) and/or peroxone process (O3+H2O2). Still, ozone-based degradation of OMPs faces several challenges. For example, the degradation mechanism and kinetics of OMPs could largely be affected by water matrix compounds which include inorganic ions and natural organic matter (NOM). pH also plays a decisive role in determining the reactivity of the oxidants (O3, H2O2, andHO•), stability and speciation of matrix constituents and OMPs and thus susceptibility of OMPs to the reactions with oxidants. There have been reviews discussing the impact of matrix components on the degradation of OMPs by advanced oxidation processes (AOPs). Nevertheless, a review focusing on scavenging mechanisms, formation of secondary oxidants and their scavenging effects with a particular focus on ozonation and peroxone process is lacking. Therefore, in order to broaden the knowledge on this subject, the database ‘Web of Science’ was searched for the studies related to the ‘matrix effect on the degradation of organic micropollutants by ozone based processes’ over the time period of 2004-2021. The relevant literature was thoroughly reviewed and following conclusions were made: i) chloride has inhibitory effects if it exits at higher concentrations or as free chlorine i.e. HOCl/ClO−. ii) The inhibitory effects of chloride, bromide, HOBr/OBr− and HOCl/ClO− are dominant in neutral and alkaline conditions and may result in the formation of secondary oxidants (e.g., chlorine atoms or free bromine), which in turn contribute to pollutant degradation or form undesired oxidation by-products such as BrO3–, ClO3– and halogenated organic products. ii) NOM may induce inhibitory or synergetic effects depending on the type, chemical properties and concentration of NOM. Therefore, more efforts are required to understand the importance of pH variation as well as the effects of water matrix on the reactivity of oxidants and subsequent degradation of OMPs.
The application of membrane technology for water treatment and reuse is hampered by the development of a microbial biofilm. Biofilm growth in micro-and ultrafiltration (MF/UF) membrane modules, on both the membrane surface and feed spacer, can form a secondary membrane and exert resistance to permeation and crossflow, increasing energy demand and decreasing permeate quantity and quality. In recent years, exhaustive efforts were made to understand the chemical, structural and hydraulic characteristics of membrane biofilms. In this review, we critically assess which specific structural features of membrane biofilms exert resistance to forced water passage in MF/UF membranes systems applied to water and wastewater treatment, and how biofilm physical structure can be engineered by process operation to impose less hydraulic resistance (“below-the-pain threshold”). Counter-intuitively, biofilms with greater thickness do not always cause a higher hydraulic resistance than thinner biofilms. Dense biofilms, however, had consistently higher hydraulic resistances compared to less dense biofilms. The mechanism by which density exerts hydraulic resistance is reported in the literature to be dependent on the biofilms’ internal packing structure and EPS chemical composition (e.g., porosity, polymer concentration). Current reports of internal porosity in membrane biofilms are not supported by adequate experimental evidence or by a reliable methodology, limiting a unified understanding of biofilm internal structure. Identifying the dependency of hydraulic resistance on biofilm density invites efforts to control the hydraulic resistance of membrane biofilms by engineering internal biofilm structure. Regulation of biofilm internal structure is possible by alteration of key determinants such as feed water nutrient composition/concentration, hydraulic shear stress and resistance and can engineer biofilm structural development to decrease density and therein hydraulic resistance. Future efforts should seek to determine the extent to which the concept of “biofilm engineering” can be extended to other biofilm parameters such as mechanical stability and the implication for biofilm control/removal in engineered water systems (e.g., pipelines and/or, cooling towers) susceptible to biofouling.
Bromide as an omnipresent matrix component in wastewater can react with ozone to form hypobromous acid (HOBr). This secondary oxidant can subsequently react with micropollutants but also with formed intermediates. Therefore, bromide and especially HOBr can highly influence the formation of transformation products (TPs). This has already been reported for the ozonation of N,N-dimethylsulfamide leading to the formation of the cancerogenic of N-nitrosodimethylamine only in bromide containing waters. In this study, the influence of different bromide and ozone concentrations on the formation of TPs during the ozonation of isoproturon (ISO), metoprolol (METO) and diclofenac (DCF) were investigated. Additionally, TPs were identified, which are formed in the direct reaction of the micropollutants with HOBr with and without subsequent ozonation. The results showed that even if the reactions of ozone with the substances should be favored bromide can highly influence the formation of TPs already at low concentrations. In summary, new TPs after the reaction with HOBr (and subsequent ozonation) could be postulated for ISO, METO and DCF. This underlines that the present water matrix can have a high influence on the formation of TPs and that these mechanisms need to be investigated further.
Reaction mechanisms of sulfate radical with bromide and organic substances can be largely altered at elevated temperature in heat-activated persulfate process due to different activation energies. This study investigated kinetics and stoichiometry of bromide oxidation in the heat-activated persulfate process. We postulated that reaction of sulfate radical with persulfate, which has relatively low reaction rate (6.3×10⁵ M–1s–1), may become an important reaction at elevated temperatures. Persulfate decomposition was inhibited in the presence of sulfate radical scavenger phenol at low temperature (40℃) whereas phenol affected persulfate decomposition only at < 50°C but not at higher temperatures. This was because the second order reaction rate constant of sulfate radical with persulfate became higher (assumed as 10¹⁰ M–1 s–1) than with phenol at a temperature > 50°C, which can be explained by a high activation energy (estimated activation energy: 311 kJ/mol). Bromate formation was inhibited in the presence of phenol. However, phenol oxidation was not affected by the presence of Br–, even though Br– reacts faster with sulfate radicals than phenol and was present in excess. This indicated that formed reactive bromine species such as Br• and Br2•– oxidize phenol under reformation of bromide. Formation of insoluble products was also observed indicating polymerization of phenol. This can be explained by lack of dissolved oxygen under conditions of heat-activation.
This is an open access article under the terms of the Creative Commons Attribution-NonCommercial-NoDerivs License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non-commercial and no modifications or adaptations are made. Reusing wastewater from oil-related industries is becoming increasingly important, especially in water-stressed oil-producing countries. Before oily wastewater can be discharged or reused, it must be properly treated, e.g., by membrane-based processes like ultrafiltration. A major issue of the applied membranes is their high fouling propensity. This paper reports on mitigating fouling inside ready-to-use ultrafiltration hollow-fiber modules used in a polishing step in oil/water separation. For this purpose, in-situ polyzwitterionic hydrogel coating was applied. The membrane performance was tested with oil nano-emulsions using a mini-plant system. The main factors influencing fouling were systematically investigated using statistical design of experiments.
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Lothar Schüller, David Schwesig
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