Fate of nutrients and trace contaminants in a large shallow soda lake. Spatial gradients and underlying processes from the tributary river to the reed belt.

Shallow lakes provide a multitude of ecosystem functions, but they are particularly vulnerable to natural and anthropogenic disturbances. Understanding the driving factors determining the fate and spatial distribution of nutrients and pollutants in such systems is fundamental to assess the impact of ongoing or future external pressures endangering their ecological integrity. This study investigates the fate of trace contaminants transported into the large shallow Lake Neusiedl, including contaminants representative of different patterns of sources and emission pathways and of environmental behavior, namely metals, pharmaceuticals, an artificial sweetener and perfluoroalkyl substances. Further, it examines the horizontal spatial distribution of nutrients, ions and physico-chemical parameters with an unprecedented detailed focus on the internal variability within the large reed belt. As described in the past e.g. for chloride, evaporation was identified as the process leading to a substantial concentration enrichment of the industrial chemical PFOA and the sweetener acesulfame K from the tributary river into the open lake. This is particularly relevant in view of the predicted future increase of evapotranspiration due to climate change. In contrast, the observed loss of diclofenac, but also of PFOS and carbamazepine suggests that the well-mixed, humic-rich and alkaline Lake Neusiedl offers favorable conditions for the photodegradation of otherwise very persistent chemicals. Another important finding, in the context of possible modifications in lake water levels due to climate change, is the fundamental role played by the connectivity between open lake and reed belt but also by the presence and characteristics of inner water areas within the reed belt region in determining the hydrochemistry of the lake system. By revealing systematic spatial patterns and by focusing on the underlying factors and processes, the understanding offered by this study is of high value for the conservation of shallow lakes.

To analyze or to throw away? On the stability of excitation-emission matrices for different water systems.

Fluorescence spectroscopy has numerous applications to characterize natural and human-influenced water bodies regarding dissolved organic matter (DOM) and contamination. Analyzing samples in a timely manner is crucial to gaining valid and reproducible excitation-emission matrices (EEM) but often difficult, specifically in transnational projects with long transport distances. In this study, eight samples of different water sources (tap water, differently polluted rivers, and wastewater treatment plant (WWTP) effluents) were stored under standardized conditions for 59 days and analyzed regularly. With this data set, the sample and fluorescence spectra stability was evaluated. Established analysis methods such as peak picking and fluorescence metrics were compared over time and benchmarked against dissolved organic carbon (DOC) and a maximal change of 10% in terms of their variability. Additional high-performance liquid chromatography (HPLC) data to identify single organic compounds provides insights into these DOM alterations and allows for conclusions about the underlying biological processes. Our results corroborate in a systematic way that the higher the organic or microbial load, the faster the sample must be processed. For all water sources, considerable changes were found between days zero and one, indicating a potential systematic bias between in-situ and laboratory measurements. The absolute signals of individual peaks vary substantially after only a few days. In contrast, relative metrics are robust for a much longer time. For specific metrics, when filtered and stored under cool and dark conditions, tap water may be stored for up to 59 days, non-polluted river water for up to 31-59 days, and WWTP effluents for up to 14-59 days. The storability thus depends both on the specific water source and the analytical plan. By systematizing our understanding of how the specific water source and DOM concentration determine the stability of samples during storage, these conclusions facilitate efforts to establish a standardized protocol.

Probabilistic fecal pollution source profiling and microbial source tracking for an urban river catchment.

We developed an innovative approach to estimate the occurrence and extent of fecal pollution sources for urban river catchments. The methodology consists of 1) catchment surveys complemented by literature data where needed for probabilistic estimates of daily produced fecal indicator (FIBs, E. coli, enterococci) and zoonotic reference pathogen numbers (Campylobacter, Cryptosporidium and Giardia) excreted by human and animal sources in a river catchment, 2) generating a hypothesis about the dominant sources of fecal pollution and selecting a source targeted monitoring design, and 3) verifying the results by comparing measured concentrations of the informed choice of parameters (i.e. chemical tracers, C. perfringensspores, and host-associated genetic microbial source tracking (MST) markers) in the river, and by multi-parametric correlation analysis. We tested the approach at a study area in Vienna, Austria. The daily produced microbial particle numbers according to the probabilistic estimates indicated that, for the dry weather scenario, the discharge of treated wastewater (WWTP) was the primary contributor to fecal pollution. For the wet weather scenario, 80-99 % of the daily produced FIBs and pathogens resulted from combined sewer overflows (CSOs) according to the probabilistic estimates. When testing our hypothesis in the river, the measured concentrations of the human genetic fecal marker were log10 4 higher than for selected animal genetic fecal markers. Our analyses showed for the first-time statistical relationships between C. perfringens spores (used as conservative microbial tracer for communal sewage) and a human genetic fecal marker (i.e. HF183/BacR287) with the reference pathogen Giardia in river water (Spearman rank correlation: 0.78-0.83, p < 0.05. The developed approach facilitates urban water safety management and provides a robust basis for microbial fate and transport models and microbial infection risk assessment.

Effect of ozonation on the biodegradability of urban wastewater treatment plant effluent.

The present work aimed to study the effect of ozonation on the organic sum parameters linked to enhanced biodegradability. Laboratory experiments were conducted with the effluent of four Austrian urban wastewater treatment plants with low food to microorganism ratios and different matrix characteristics. Biochemical oxygen demand over 5 days (BOD5) was measured before ozonation and after application of different specific ozone doses (Dspec) (0.4, 0.6 and 0.8 g O3/g DOC). Other investigated organic parameters comprised chemical oxygen demand (COD), dissolved organic carbon (DOC), UV absorption at 254 nm (UV254), which are parameters that are applied in routine wastewater analysis. Carbamazepine and benzotriazole were measured as reference micropollutants. The results showed a dose-dependent increase in biological activity after ozonation; this increase was linked to the enhanced biodegradability of substances that are recalcitrant to biodegradation in conventional activated sludge treatment. The highest relative change was determined for BOD5, which already occurred between 0 and 0.4 g O3/g DOC for all samples. Increasing the Dspec to 0.6 and 0.8 g O3/g DOC resulted in a less pronounced increase. DOC was not substantially decreased after ozonation, which was consistent with a low reported degree of mineralization, while partial oxidation led to a quantifiable decrease in COD (7 to 17%). Delta UV254 and the decline in specific UV absorption after ozonation clearly correlated with Dspec. In contrast, for COD and biodegradable DOC (BDOC), a clear dose-response pattern was identified only after exposure to BOD5 measurement. Indications for improved biodegradability were further supported by the rise in the BOD5/COD ratio. The results indicated that subsequent biological processes have a higher degradation potential after ozonation. The further reduction in biodegradable organic carbon emission by the combination of ozonation and biological post treatment represents another step towards sustainable water resource management in addition to micropollutant abatement.

Ozone as oxidizing agent for the total oxidizable precursor (TOP) assay and as a preceding step for activated carbon treatments concerning per- and polyfluoroalkyl substance removal.

Several thousands of highly persistent per- and polyfluoroalkyl substances (PFAS) exist and it is therefore challenging to analytically determine a larger spectrum of these compounds simultaneously in one sample. It is even more difficult to efficiently remove mobile PFAS in wastewater treatment plants (WWTPs) to protect the receiving waters. The total oxidizable precursor (TOP) assay is an approach that enables the detection of the total PFAS content in a sample via oxidation of precursors, followed by subsequent analysis of the perfluoroalkyl acid (PFAA) concentration before and after oxidative processes. Activated carbon combined with a preceding ozonation step is considered a promising tool for the removal of micropollutants but considering PFAS removal efficiencies in effluents for this process combination more information is required. The focus of the study was to implement and assess the TOP assay with ozone as oxidizing agent to estimate the total PFAS content in a WWTP effluent. Additionally, granular activated carbon (GAC) and powdered activated carbon (PAC) with a preceding ozonation step was tested for the removal efficiencies for 22 PFAS. For the TOP assay the obtained accordance in molarity using spiked tap water as quality control was 95.2% (15 mg O3/L) and 99.1% (6 mg O3/L). Applying the TOP assay, an estimated total PFAS content of 840 ng/L was determined in the respective effluent, which was 91.1% higher than obtained by target PFAS analysis, implying the presence of unknown precursors not included in common monitoring. While all treatment techniques that included ozone or a preceding ozonation step solely transformed precursors and long-chain perfluoroalkyl acids (PFAA, i.e., >C9) to shorter congeners, PAC was the only tested water treatment application that was able to remove 19.3% of the total PFAS molarity.

A method to estimate the direct nitrous oxide emissions of municipal wastewater treatment plants based on the degree of nitrogen removal.

The greenhouse gas nitrous oxide (N2O) is produced in activated sludge tanks as a byproduct of nitrification and heterotrophic denitrification. Insufficient knowledge on how microbiological N2O generation and degradation pathways impact N2O emissions in activated sludge tanks still hampers the development of effective mitigation strategies. Our research contributes to overcome this gap by quantifying N2O emissions through extensive measurement campaigns at ten full-scale wastewater treatment plants and correlating them to relevant operating parameters by multivariate regression analysis. Measurements revealed that N2O production depends mainly on the activity of nitrifying bacteria and is triggered by high ammonium concentrations. In contrast, well-performing heterotrophic denitrification plays a key role as a sink of N2O in activated sludge tanks. Following these patterns, low loaded plants achieving high nitrogen removal (83-92%) exhibited the lowest N2O emission intensity (0.0012 ± 0.001 kg N2O-N emitted per kg TKN in the influent wastewater). The regression analysis corroborated these results by revealing a negative linear correlation between the N2O emission factor and the total nitrogen removal degree of the plants. The regression model represents a novel estimation method that links N2O emissions with plant performance and provides a significant improvement over approaches applying fixed N2O emission factors.

Capillary electrophoresis for continuous nitrogen quantification in wastewater treatment processes.

A water quality analyzer based on the working principle of capillary electrophoresis (CE) was developed to determine ionic inorganic nitrogen compounds contained in wastewater samples. The instrument provides simultaneous quantification of anions and cations by superimposing hydrodynamic pumping with electrokinetic motion. It features a single separation capillary with contactless conductivity detection and a sequential injection manifold for fluid handling. Dynamic adaption of the system calibration was enabled by the use of a high precision pressure regulator to cover a wide measurement range showing low relative standard deviations (< 2 %) and high measurement accuracy comparable to conventional wastewater analyzers. The prototype is transportable, integrated in a 19 in. rack and connected to a membrane filter system developed for direct sample aspiration in the wastewater process. For operation on site, only a power supply and a network connection for remote control is necessary. Continuous operation was demonstrated over 24 h at the aeration tank of a pilot scale wastewater treatment plant at TU Wien and a good correlation with laboratory results was achieved. At this time, there is no device available, on the market, to analyze all nitrogen species in one assembly with limited hardware complexity and chemical demand. This entails a significant step forward towards automated water quality monitoring with respect to the implementation of new advanced wastewater treatment technologies.

Spatiotemporal resolved sampling for the interpretation of micropollutant removal during riverbank filtration.

Riverbank filtration (RBF) systems along rivers are widely used as public water supplies. In these systems, many organic micropollutants (OMPs) are attenuated, but some compounds have shown to be rather persistent. Their fate and transport has been studied in RBF sites along lakes and small rivers, but not extensively along large and dynamic rivers. Therefore, the influence of flood events on OMP behavior in these large and dynamic RBF sites was investigated. Monthly samples were taken from surface- and groundwater up to a distance of 900 m from the riverbank of the Danube from March 2014 till May 2016. Two flood events were sampled more extensively nearby the river. Results showed that changes in flow conditions in the river not only caused changes in OMP concentrations, but also in their load. It was seen that the load of benzotriazole, carbamazepine and sulfamethoxazole in the river increased with increasing river discharges. After a relatively long, oxic groundwater passage, several OMPs were reduced. In contrast to previous work, we found that benzotriazole was almost fully removed under oxic conditions. When entering the aquifer, benzotriazole concentrations were significantly reduced and at a distance of 550 m from the river, >97% was degraded. Carbamazepine and sulfamethoxazole showed relatively persistent behavior in the aquifer. The concentrations measured during flood events were in the same range as seasonal sampling. Furthermore concentrations in the groundwater were higher during these events than in the Danube and can reach further into the aquifer. During flood events some highly degradable compounds (i.e. diclofenac) were found up to a distance of 24 m from the river. These results implied that drinking water utilities with RBF wells in oxic, alluvial aquifers located close to highly dynamic rivers need to consider a potential reduction in groundwater quality during and directly after flood events.

Occurrence and levels of micropollutants across environmental and engineered compartments in Austria.

Occurrence and concentration of a broad spectrum of micropollutants are investigated in Austrian river catchments, namely polycyclic aromatic hydrocarbons (PAHs), polybrominated diphenyl ethers (PBDEs), organotin compounds, perfluoroalkyl acids (PFAAs) and metals. The parallel analysis across multiple environmental and engineered compartments sheds light on the ratio of dissolved and particulate transport and on differences in concentration levels between point and diffuse emission pathways. It is found that some PAHs and organotins are present in rivers, groundwater and bulk deposition at higher concentrations than in municipal wastewater effluents. Among PFAAs and metals, highest concentrations were recorded either in atmospheric deposition or in discharges from wastewater treatment plants. The relevance of the analysis across compartments is best shown by the case of perfluorooctanesulfonic acid (PFOS). Despite municipal wastewater effluents being the emission pathway with highest concentrations, this study reveals that not only rivers, but also atmospheric deposition and groundwater sometimes exceed the environmental quality standard for surface waters. Moreover, this work reveals partially counterintuitive patterns. In rivers with treated wastewater discharges, increasing levels of dissolved compounds were measured at rising flow conditions, whereas the opposite would be expected owing to the dilution effect. This might derive from the mobilisation from soil or suspended particulate matter or rather find its explanation in high concentrations in atmospheric deposition. These hypotheses require however being tested through targeted studies. Additional future research includes the analysis of how regional or catchment specific characteristics might alter the relative importance of different emission pathways, and the modelling of emission and river loads to assess their relative contribution to river pollution.

Optimization of ozonation and peroxone process for simultaneous control of micropollutants and bromate in wastewater.

The study aims to simultaneously control micropollutants and bromate formations by using ozonation and peroxone process. The batch experiments were run with variations in specific ozone dose (SOD) and hydrogen peroxide-to-ozone (H2O2/O3) ratio. Based on the removal by ozonation and peroxone, micropollutants were categorized into three groups: non-reactive compounds (i.e. amidotrizoate), moderately reactive compounds (i.e. metoprolol, acesulfame potassium, bezafibrate, and benzotriazole), and highly reactive compounds (i.e. carbamazepine and diclofenac). For ozonation and peroxone process, the removals for highly reactive compounds and moderately reactive compounds were 82-99% and 29-99%, respectively. The removal of amidotrizoate was not observed in this study. The effect of ozonation on micropollutant removals was similar to the peroxone process. However, differences in bromate formation were observed. Bromate formation depended on the SOD, while addition of hydrogen peroxide suppressed the bromate formation. The peroxone process at the H2O2/O3 ratio of 0.3 was recommended to bromide-containing water below 100 µg·L-1 for simultaneous control of micropollutants and bromate. Enhancement in micropollutant removals, except for the non-reactive groups, was achieved with either higher SOD or the addition of hydrogen peroxide to ozonation. The micropollutant removal predicted from the second-order kinetic reaction with ozone and •OH exposures was higher than the observed data.

The seasonal dynamics of the stream sources and input flow paths of water and nitrogen of an Austrian headwater agricultural catchment.

Our study examines the source aquifers and stream inputs of the seasonal water and nitrogen dynamics of a headwater agricultural catchment to determine the dominant driving forces for the seasonal dynamics in the surface water nitrogen loads and concentrations. We found that the alternating aquifer contributions throughout the year of the deep and shallow aquifers were the main cause for the seasonality of the nitrate concentration. The deep aquifer water typically contributed 75% of the total outlet discharge in the summer and 50% in the winter when the shallow aquifer recharges due to low crop evapotranspiration. The shallow aquifer supplied the vast majority of the nitrogen load to the stream due to the significantly higher total nitrogen concentration (11 mg-N/l) compared to the deep aquifer (0.50 mg-N/l). The main stream input pathway for the shallow aquifer nitrogen load was from the perennial tile drainages providing 60% of the total load to the stream outlet, while only providing 26% of the total flow volume. The diffuse groundwater input to the stream was the largest input to the stream (39%), but only supplied 27% to the total nitrogen load as the diffuse water was mostly composed of deep aquifer water.

Adsorption of bisphenol-A, 17 beta-estradiole and 17 alpha-ethinylestradiole to sewage sludge.

Adsorption of bisphenol-A (CAS 85-05-7), 17 beta-estradiole (CAS 50-28-2) and 17 alpha-ethinylestradiole (CAS 57-63-6) to activated and to inactivated sludge from wastewater treatment plants (WWTPs) was investigated, thus allowing to distinguish between pure adsorption and biosorption. For the investigated substances the determination of the adsorption kinetics is based on experiments performed according to the OECD guideline 106 and on free concentration measurements in the liquid phase. The description of the adsorption behaviour occurred via Freundlich Adsorption Isotherms. Additionally specific adsorption coefficients KD, KOM and KOC were calculated. The results of these calculations were compared to KOC values obtained with a HPLC method according to the OECD guideline 121. All substances showed a high adsorption affinity to the adsorbent and in spite of the application of very high initial concentrations no saturation level could be reached. Within a contact time of 24 h, no difference between the adsorption to activated and inactivated sludge could be detected. The calculated KD values were within a range of about KD = 1000 l kg(-1) for the investigated compounds and showed a clear concentration dependency in the case of bisphenol-A. Adsorption was also found to depend on pH. The experimentally determined KOC values of the investigated substances were significantly higher than the results obtained with the HPLC method described in OECD guideline 121.