Coupling a pathway-oriented approach with tailor-made monitoring as key to well-performing regionalized modelling of PFAS emissions and river concentrations.

Surface water pollution with poly- and perfluorinated compounds (PFAS) is a well-recognized problem, but knowledge about contribution of different emission pathways, especially diffuse ones, is very limited. This study investigates the potential of the pathway oriented MoRE model in shedding light on the relevance of different emission pathways on regional scale and in predicting concentrations and loads in unmonitored rivers. Modelling was supported with a tailor-made monitoring programme aimed to fill gaps on PFAS concentration in different environmental compartments. The study area covers the whole Austrian territory including some additional transboundary catchments and it focuses on perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS). These two PFAS are regulated and therefore their production and use in Europe are currently decreasing. Nevertheless, these compounds are still emitted into the environment via legacy pollution and as transformation products from other PFAS. These two compounds were selected for this study in view of the larger information availability compared to other PFAS. Despite considerable uncertainties in the input data, model validations show that this approach performs significantly better than previous modelling frameworks based on population-specific emission factors, population density and wastewater treatment plant information. The study reveals the predominance of emissions via municipal wastewater treatment plants for PFOS and a relevant role of diffuse emission pathways for PFOA. Results suggest that unpaved areas contribute the biggest share to total diffuse emissions, but the estimation of these pathways is affected by the highest uncertainty in the input data and requires better input data from monitoring. Once the currently growing substance-specific data sets on the concentration of PFAS, others than PFOS and PFOA, in different environmental compartments, will reach an adequate quality, the model presented here will be easily applicable to them.

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.

Evaluating the success of sewer reconstruction by using carbamazepine as anthropogenic marker in groundwater.

The antiepileptic drug carbamazepine is a useful anthropogenic marker in groundwater to detect and quantify sewer exfiltration. In 2003 its application on a city wide scale enabled the identification of a trunk sewer in extremely bad structural status with an exfiltration (of wastewater into groundwater) rate in the adjacent area of around 5% compared to an average of approximately 1% in other parts of the city. After a reconstruction of the trunk sewer investigations were carried out again in 2008. Due to the reconstruction a decrease in exfiltration to roughly 3% could be achieved, which equals a reduction of exfiltration by about 45%. Thus carbamazepine emerged as suitable anthropogenic marker to assess sewer exfiltration and to evaluate the success of reconstruction measurements on a regional scale.

Micropollutant removal during biological wastewater treatment and a subsequent ozonation step.

The design criteria for wastewater treatment plants (WWTP) and the sludge retention time, respectively, have a significant impact on micropollutant removal. The upgrade of an Austrian municipal WWTP to nitrogen removal (best available technology, BAT) resulted in increased elimination of most of the analyzed micropollutants. Substances, such as bisphenol-A, 17alpha-ethinylestradiol and the antibiotics erythromycin and roxithromycin were only removed after the upgrade of the WWTP. Nevertheless, the BAT was not sufficient to completely eliminate these compounds. Thus, a pilot scale ozonation plant was installed for additional treatment of the effluent. The application of 0.6 g O(3) g DOC(-1) increased the removal of most of the micropollutants, especially for compounds that were not degraded in the previous biological process, as for example carbamazepine and diclofenac. These results indicated that the ozonation of WWTP effluent is a promising technology to further decrease emissions of micropollutants from the treatment process.

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.