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Targeted and untargeted analysis of organic contaminants from on-site sewage treatment facilities: Removal, fate and environmental impact
Umeå University, Faculty of Science and Technology, Department of Chemistry.
2018 (English)Doctoral thesis, comprehensive summary (Other academic)Alternative title
Riktad och förutsättningslös analys av organiska föroreningar från små avlopp : Reningseffektivitet, transport och miljöpåverkan (Swedish)
Abstract [en]

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.

Place, publisher, year, edition, pages
Umeå: Umeå universitet , 2018. , p. 77
Keywords [en]
decentralized sewage treatment, wastewater, surface water, environmental fate, bioavailability, removal efficiency, mass fluxes, biochar, environment, GC×GC-MS, LC-IM-MS, mass spectrometry, contaminants, pollutants, prioritization, non-target analysis, screening
National Category
Analytical Chemistry Environmental Sciences
Research subject
Analytical Chemistry
Identifiers
URN: urn:nbn:se:umu:diva-144262ISBN: 978-91-7601-836-1 (print)OAI: oai:DiVA.org:umu-144262DiVA, id: diva2:1178364
Public defence
2018-02-23, KBE301 (Lilla hörsalen), Kemiskt Biologiskt Centrum (KBC), Umeå, 09:00 (English)
Opponent
Supervisors
Available from: 2018-02-02 Created: 2018-01-29 Last updated: 2018-06-09Bibliographically approved
List of papers
1. Non-target screening and prioritization of potentially persistent, bioaccumulating and toxic domestic wastewater contaminants and their removal in on-site and large-scale sewage treatment plants
Open this publication in new window or tab >>Non-target screening and prioritization of potentially persistent, bioaccumulating and toxic domestic wastewater contaminants and their removal in on-site and large-scale sewage treatment plants
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2017 (English)In: Science of the Total Environment, ISSN 0048-9697, E-ISSN 1879-1026, Vol. 575, p. 265-275Article in journal (Refereed) Published
Abstract [en]

On-site sewage treatment facilities (OSSFs), which are used to reduce nutrient emissions in rural areas, were screened for anthropogenic compounds with two-dimensional gas chromatography–mass spectrometry (GC × GC–MS). The detected compounds were prioritized based on their persistence, bioaccumulation, ecotoxicity, removal efficiency, and concentrations. This comprehensive prioritization strategy, which was used for the first time on OSSF samples, ranked galaxolide, α-tocopheryl acetate, octocrylene, 2,4,7,9-tetramethyl-5-decyn-4,7-diol, several chlorinated organophosphorus flame retardants and linear alkyl benzenes as the most relevant compounds being emitted from OSSFs. Twenty-six target analytes were then selected for further removal efficiency analysis, including compounds from the priority list along with substances from the same chemical classes, and a few reference compounds. We found significantly better removal of two polar contaminants 2,4,7,9-tetramethyl-5-decyn-4,7-diol (p = 0.0003) and tris(2-butoxyethyl) phosphate (p = 0.005) in soil beds, a common type of OSSF in Sweden, compared with conventional sewage treatment plants. We also report median removal efficiencies in OSSFs for compounds not studied in this context before, viz. α-tocopheryl acetate (96%), benzophenone (83%), 2-(methylthio)benzothiazole (64%), 2,4,7,9-tetramethyl-5-decyn-4,7-diol (33%), and a range of organophosphorus flame retardants (19% to 98%). The environmental load of the top prioritized compounds in soil bed effluents were in the thousands of nanogram per liter range, viz. 2,4,7,9-tetramethyl-5-decyn-4,7-diol (3000 ng L− 1), galaxolide (1400 ng L− 1), octocrylene (1200 ng L− 1), and α-tocopheryl acetate (660 ng L− 1).

Place, publisher, year, edition, pages
Elsevier, 2017
Keywords
Two-dimensional gas chromatography-mass spectrometry, Non-target analysis, Ranking, Decentralized sewage treatment, Removal efficiencies, Organic micropollutants
National Category
Chemical Sciences Environmental Sciences
Identifiers
urn:nbn:se:umu:diva-128756 (URN)10.1016/j.scitotenv.2016.09.135 (DOI)000390373400028 ()27744155 (PubMedID)
Available from: 2016-12-14 Created: 2016-12-14 Last updated: 2018-06-09Bibliographically approved
2. Persistence, mobility and bioavailability of emerging organic contaminants discharged from sewage treatment plants
Open this publication in new window or tab >>Persistence, mobility and bioavailability of emerging organic contaminants discharged from sewage treatment plants
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2018 (English)In: Science of the Total Environment, ISSN 0048-9697, E-ISSN 1879-1026, Vol. 612, p. 1532-1542Article in journal (Refereed) Published
Abstract [en]

Little is known about the impact of emissions of micropollutants from small and large-scale sewage treatment plants (STPs) on drinking water source areas. We investigated a populated catchment that drains into Lake Malaren, which is the drinking water source for around 2 million people including the inhabitants of Stockholm, Sweden. To assess the persistence, mobility, bioavailability and bioaccumulation of 32 structurally diverse emerging organic contaminants, sediment, integrated passive and grab water samples were collected along the catchment of the River Fyris, Sweden. The samples were complemented with STP effluent and fish samples from one sampling event. Contaminants identified as persistent, mobile, and bioavailable were 4,6,6,7,8,8-hexamethyl-1,3,4,7-tetrahydrocyclopenta[g] isochromene (galaxolide), 2,4,7,9-tetramethyl-5-decyn-4,7-diol, tris(2-chloroethyl) phosphate, tris(1,3-dichloro-2-propyl) phosphate, and tris(1-chloro-2-propyl) phosphate. Galaxolide and 2,4,7,9-tetramethyl-5-decyn-4,7-diol were additionally found to be bioaccumulative, whereas n-butylbenzenesulfonamide was found to be only persistent and mobile. The total median mass flux of the persistent and mobile target analytes from Lake Ekoln into the drinking water source area of Lake Malaren was estimated to be 27 kg per year. Additionally, 10 contaminants were tentatively identified by non-target screening using NIST library searches and manual review. Two of those were confirmed by reference standards and further two contaminants, propylene glycol and rose acetate, were discharged from STPs and travelled far from the source. Attenuation of mass fluxes was highest in the summer and autumn seasons, suggesting the importance of biological degradation and photodegradation for the persistence of the studied compounds.

Place, publisher, year, edition, pages
Elsevier, 2018
Keywords
Mass fluxes, Fate, Sediment-water distribution, Bioaccumulation, Non-target screening, GC x GC-HRMS
National Category
Environmental Sciences
Identifiers
urn:nbn:se:umu:diva-141837 (URN)10.1016/j.scitotenv.2017.09.006 (DOI)000413313700151 ()28915547 (PubMedID)
Available from: 2017-11-14 Created: 2017-11-14 Last updated: 2018-06-09Bibliographically approved
3. Mass fluxes per capita of organic contaminants from on-site sewage treatment facilities
Open this publication in new window or tab >>Mass fluxes per capita of organic contaminants from on-site sewage treatment facilities
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(English)Manuscript (preprint) (Other academic)
Abstract [en]

This study is the first attempt to quantify environmental fluxes per capita of organic contaminants discharged from on-site sewage treatment facilities (OSSFs) in affected recipients. Five sites were monitored around the River Fyris in Sweden: three mainly affected by OSSFs and two mainly affected by municipal sewage treatment plants (STPs). Gas chromatography-mass spectrometry was used to determine environmental concentrations of 30 anthropogenic contaminants, including organophosphorus compounds, rubber and plastic additives, UV stabilizers, fragrances, surfactant ingredients and polycyclic aromatic hydrocarbons. Uni- and multivariate statistical analysis of the most frequently detected contaminants showed that median fluxes per capita of tris(1,3-dichloro-2-propyl) phosphate, tris(1-chloro-2-propyl) phosphate, tris(2-chloroethyl) phosphate, and n-butylbenzene sulfonamide were similar at OSSF and STP sites, but the mass fluxes per capita of tris-(2-butoxyethyl) phosphate, 2-(methylthio)benzothiazole, and galaxolide, were significantly lower (~2 to 3-fold) at OSSF sites than at STP sites (Mann-Whitney, α = 0.05). Differences between these sites were larger in samples collected in summer and autumn than in samples collected in winter. Deviations likely originated from differences in treatment technology and distances between source and sampling sites. Further studies are needed to characterize mass fluxes per capita of contaminants in waters that directly receive discharges from OSSFs.

Keywords
Decentralized wastewater treatment systems, environmental load, surface water, diffuse sources, GC×GC-HRMS
National Category
Analytical Chemistry
Identifiers
urn:nbn:se:umu:diva-144259 (URN)
Available from: 2018-01-29 Created: 2018-01-29 Last updated: 2018-06-09
4. Comprehensive assessment of organic contaminant removal from on-site sewage treatment facility effluent by char-fortified filter beds
Open this publication in new window or tab >>Comprehensive assessment of organic contaminant removal from on-site sewage treatment facility effluent by char-fortified filter beds
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(English)Manuscript (preprint) (Other academic)
Abstract [en]

The removal of organic contaminants from wastewater using cost-efficient and easily accessible methods have been increasingly studied in recent years. Most studies have focused on municipal sewage treatment plants; however, our study investigated treatment with char-fortified filter beds for on-site sewage treatment facilities (OSSFs). OSSFs are commonly used in rural and semi-urban areas all over the world to treat wastewater to reduce eutrophication and water-related diseases. To screen for a wide range of organic contaminants in order to improve the understanding of wastewater treatment efficiency and molecular properties, samples were taken from an OSSF field study site that used three filter types: sand, char-fortified sand, and char-fortified gas concrete. First, we screened for organic contaminants with state-of-the-art gas chromatography and liquid chromatography mass spectrometry-based targeted and untargeted analysis and then we developed quantitative structure-property relationship models to find the key molecular features responsible for the removal of organic contaminants. We identified 74 compounds, of which 24 were confirmed with reference standards. Amongst these 74 compounds were plasticizers, UV stabilizers, fragrances, pesticides, surfactant and polymer impurities, pharmaceuticals and their metabolites, and many biogenic compounds. Sand filters that are sometimes used as a last treatment step in OSSFs can remove hydrophobic contaminants. The addition of biochar significantly increases the removal of these and a few hydrophilic compounds (Wilcoxon signed-rank test, α = 0.05). Gas concrete did not appear to be suitable for the removal of organic contaminants. This study showed that, besides hydrophobic effects, biodegradation is the most important removal pathway in long-term field applications. However, further improvements are necessary to remove very hydrophilic contaminants as they were not removed with sand and biochar-fortified sand.

Keywords
Screening, decentralized wastewater treatment systems, GC×GC-HRMS, LC IM HRMS, biochar, quantitative structure-property relationship
National Category
Analytical Chemistry
Identifiers
urn:nbn:se:umu:diva-144261 (URN)
Available from: 2018-01-29 Created: 2018-01-29 Last updated: 2018-06-09

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