Targeted and untargeted analysis of organic contaminants from on-site sewage treatment facilities : Removal, fate and environmental impact

Sammanfattning: On-site sewage treatment facilities (OSSFs) are widely used all over the world to treat wastewater when large-scale sewage treatment plants (STPs) are not economically feasible. Although there is great awareness that the release of untreated wastewater into the environment can lead to water-related diseases and eutrophication, little is known about organic contaminants and their removal by OSSFs, environmental load and fate. Thus, this PhD thesis aims to improve the knowledge about treatment efficiencies in current OSSFs, the environmental impact and fate of contaminants released from OSSFs, as well as how biochar fortification in sand filter (soil beds) OSSFs might increase removal of these contaminants. State-of-the-art analytical techniques for untargeted and targeted analyses were used and the results evaluated with univariate and multivariate statistics.Environmentally-relevant contaminants discharged from OSSFs were identified using untargeted analysis with two-dimensional gas chromatography mass spectrometry (GC×GC-MS) and a MS (NIST) library search in combination with a prioritization strategy based on environmental relevance. A method was successfully developed for the prioritized contaminants using solid phase extraction and GC×GC-MS, and the method was also applicable to untargeted analysis. This method was applied to several studies. The first study compared treatment efficiencies between STP and soil beds and showed that treatment efficiencies are similar or better in soil beds, but the removal among the same type of treatment facilities and contaminants varied considerably. Hydrophilic contaminants were generally inadequately removed in both types of treatment facilities and resulted in effluent levels in the nanogram per liter range.Additionally, several prioritized and sometimes badly removed compounds were found to be persistent, mobile, and bioavailable and two additional, untargeted contaminants identified by the NIST library search were potentially mobile. These contaminants were also found far from the main source, a large-scale STP, at Lake Ekoln, which is part of the drinking water reservoir Lake Mälaren, Sweden. The study also showed that two persistent, mobile and bioavailable contaminants were additionally bioaccumulating in perch. Sampling for this study was carried out over several seasons in the catchment of the River Fyris. Parts of this catchment were affected by OSSFs, other parts by STPs. Potential ecotoxicological risks at these sites were similar or higher at those affected by STPs compared to those affected by OSSFs. Mass fluxes per capita were calculated from these levels, which were higher at STP-affected than at OSSF-affected sites in summer and autumn, but not in winter. Possibly, the diffuse OSSF emissions occur at greater average distances from the sampling sites than the STP point emissions, and OSSF-affected sites may consequently be more influenced by fate processes.The studies carried out suggested that there is a need to improve current treatment technologies for the removal of hydrophilic contaminants. Thus, the final study of this thesis investigated char-fortified sand filters (soil beds) as potential upgrades for OSSFs using a combination of advanced chemical analysis and quantitative structure-property relationship modeling. Removal efficiencies were calculated from a large variety of contaminants that were identified by untargeted analysis using GC×GC-MS and liquid chromatography ion mobility mass spectrometry as well as library searches (NIST and Agilent libraries). On average, char-fortified sand filters removed contaminants better than sand, partly due to an enhanced removal of several hydrophilic contaminants with heteroatoms. After a two-year runtime, sorption and particularly biodegradation must have contributed to the removal of these compounds.Generally, the combination of targeted and untargeted analysis has proven valuable in detecting a large variety of organic contaminants, as well as unexpected ones. The results imply that OSSFs have similar or better removal efficiencies, similar or lower environmental risks and similar or lower mass fluxes per capita, compared to STPs. Biochar fortification can improve the removal of organic contaminants in soil beds, but further research is needed to find technologies that reduce the discharge of all types of organic contaminants.