Per- and polyfluoroalkyl substances (PFASs) are a group of emerging chemicals which havereceived increasing attention due to their toxicity, persistent properties, and global distribution.In this study, sorption coefficients (Kd and KOC) of PFASs in an industrial site in Sweden wereevaluated. Sorption is a measures of the mobility of a substance in the subsurface, and is a keyfactor in environmental risk assessments. Sorption coefficients were calculated both from fieldsamples processed in laboratory batch tests, and from a simplified approach involving the totalconcentrations in soil and groundwater (field-derived). Soil was sampled from two locations ofthe site; C8 and M6. Field-derived values were calculated based on concentrations which werehistorically measured. The aim was to compare the two methods, and to compare the valueswith literature values as well as guideline sorption values established by the SwedishGeotechnical Institute (SGI). Sorption coefficients for PFHxA, PFHpA, PFOA, PFHxS, PFOS, 6:2 FTS and PFBS could beestablished. Results showed that laboratory-derived sorption coefficients were significantlyhigher than field-derived sorption coefficients. Laboratory-derived sorption values were alsohigher than to SGI’s preliminary sorption values. Comparing C8 and M6 KOC values toliterature values, PFHpA, PFHxA, and PFBS exhibit values above literature values. PFOA,PFHxS, PFOS exhibit KOC values within the range of literature values. According to thesorption coefficients, predictive scenarios of leaching through the unsaturated zone weremodelled, and it was concluded that leaching was higher in M6 compared to C8. The resultsalso showed that an increase in precipitation increased the leaching. / Per- och polyfluorerade alkylsubstanser (PFAS) är en grupp nyligen uppkomna kemikalier somhar fått ökad uppmärksamhet pga. deras toxicitet, ihärdiga egenskaper och globala utbredning.Detta examensarbete har studerat fördelningskoefficienter (Kd och KOC) för PFAS inom ettindustriområde i Sverige. Fördelningskoefficienter är ett mått på mobilitet av en substans iunderjorden, och det är en viktig komponent i riskbedömningar inom förorenad mark.Fördelningskoefficienter beräknades dels utifrån jordprover som tagits i fält och analyserats ilaboratorium med extraktionsmetoder, och dels utifrån ett förenklat tillvägagångssätt därberäkning skett med hjälp av tidigare uppmätta koncentrationer i jord och grundvatten.Jordprover från två områden inom industriområdet; C8 och M6, togs och analyserades.Fältbaserade fördelningskoefficienter beräknades utifrån koncentrationer som tidigare mättsvid brunnsinstallation och vid grundvattenövervakning. Målet med studien var att jämföra detvå metoderna, och dessutom jämföra fördelningskoefficienterna med motsvarande i värdenlitteraturen samt riktvärden för fördelningskoefficienter som Statens Geotekniska Institutet(SGI) arbetet fram. Fördelningskoefficienter för PFHxA, PFHpA, PFOA, PFHxS, PFOS, 6:2 FTS and PFBS kundeberäknas. Resultatet visade att laboratorie-baserade fördelningskoefficienter var betydligthögre än fältbaserade fördelningskoefficienter. Laboratorie-baserade fördelningskoefficientervar även högre än de preliminära riktvärden för fördelningskoefficienter som SGI etablerat. Vidjämförelse av fördelningskoefficienter för C8 och M6 kunde det konstateras att PFHpA,PFHxA, and PFBS hade högre värden än motsvarande i litteraturen. PFOA, PFHxS, PFOSvisade på värden som var inom intervallet av värdena från litteraturen. Med hjälp av deberäknade fördelningskoefficienterna modellerades prediktiva utlaknings-scenarier. Utifrånresultatet sker utlakningen i större grad i M6 jämfört med C8. Utlakningen ökade även vidförhöjd nederbörd.

Per- och Polyfluorerade alkylsubstanser (PFAS) är syntetiskt framställda organiska föreningar som har använts i stor utsträckning i konsument- och industriprodukter. PFAS-substanser besitter attraktiva egenskaper såsom resistans mot väta, fett, fläckar och är dessutom värmetåliga. De används i bland annat brandskum, smink, vattentäta kläder med ”andas-funktion”, möbler och non- stickstekpannor. Den senaste forskningen har dock visat att PFAS utgör en fara för levande organismer och miljön. Vissa PFAS-substanser har klassats som persistenta, bioackumulativa och toxisk (PBT), samt väldigt persistenta och väldigt bioaccumulativa (vPvB).Existerande forskning har fokuserat på beteendet hos PFAS i olika miljöer. Dock finns det en kunskapslucka när det gäller hur dessa PFAS-substanser beter sig under termiska behandlingsprocesser, samt förbränningsgraden i kommersiella förbränningsanläggningar vid temperaturerna 850–950 °C. I detta projekt undersöks därför nedbrytningsgraden av PFAS genom förbränning samt bildning av potentiellt farliga biprodukter efter förbränning. För att genomföra denna studie skulle förbränning av PFAS-haltigt avloppsslam i en pilotskalig bubblande fluidiserad bädd (BFB) genomföras. På grund av hinder utfördes experimenten i stället i en konventionell och simpel laboratorieugn. Dessutom genomfördes en litteraturstudie för att undersöka bildandet av potentiellt farliga biprodukter efter förbränning av PFAS. Denna studie har visat att termisk behandling genom förbränning är en effektiv metod för att behandla PFAS i avloppsslam med reduktion under kvantifieringsgränserna. Undersökning av potentiellt farliga biprodukter baserat på litteraturstudier har visat att kortkedjiga PFCAs var mest förekommande i aska, vätska och gasformiga rester efter termisk behandling. Några undersökningar tyder på att termisk behandling av PFAS-haltigt material möjligen resulterar i ozonnedbrytande ämnen. Utifrån den genomförde litteraturstudien i detta projekt saknas starka bevis för att kunna påstå att det bildas ozonnedbrytande ämnen under förbränning av PFAS. / Per- and polyfluoroalkyl substances (PFAS) are man-made organic compound widely used in consumer and industrial products. They exhibit attractive properties such as resistance to water, heat, and grease. Therefore, PFAS are used in fire foam, non-stick pans, water-resistant clothes, make-up, and furniture. Recent studies have revealed that PFAS substances can be harmful to humans, animals, and the environment. Some PFAS substances have, therefore, been classified as persistent, bioaccumulative, and toxic (PBT), and very persistent and very bioaccumulative (vPvB). This means that PFAS resists degradation, accumulates in living organisms and biota, and inherits toxic effects. In previous and current research, the focus has been on the behavior of PFAS in different environmental settings. However, there is a gap in research on how these PFAS substances behave during thermal treatment processes in commercial facilities at temperatures of 850-950 °C and how effective the thermal degradation is. This project investigates the effectivity of thermal degradation via combustion and the fate of PFAS post-combustion, focusing on the formation of potentially hazardous by-products. Therefore, the combustion of PFAS-containing sewage sludge in a bench- scale bubbling fluidized bed (BFB) was to be conducted to fulfill the objective of this study. Due to hindrances, the experiments were performed in a conventional furnace furnace instead. Also, a literature study was conducted to investigate the fate of PFAS after combustion. From this study, it was concluded that thermal treatment via combustion at temperatures 850 and 950 °C is an effective method to degrade PFAS in sewage sludge. Also, the literature study investigation revealed that persistent short-chain PFCAs were most abundant in the ash, liquid, and gaseous residues after thermal treatment. A few investigations indicate that thermal treatment of PFAS-containing matter possibly results in ozone-depleting compounds. Based on the conducted literature study, there is a lack of strong evidence that supports the claim of the formation of ozone- depleting compounds during combustion of PFAS.

Fluorkemi används på varselkläder i syfte för att skydda textilen mot smuts, vatten, fett och olja. Kemikalierna är skadliga för människor och miljö, de är dessutom mycket svårnedbrutna eller så bryts de inte ner överhuvudtaget. Kemikalierna är utvecklade av människor och delas upp i perfluorerade och polyfluorerade ämnen (PFAS). PFAS klassificeras också som PBT-ämnen, vilket står för att de är persistenta, bioackumulerande och toxiska. Studien är utförd i ett samarbete med Tranemo Textil AB, där behovet av fluorkarbonberedning på varselkläder undersökts. Syftet med studien är att undersöka utifrån användning och tvättprocess om fluorkarbonberedning är essentiell på varselkläder. Genom intervjuer med experter och tvätterier har studien fått fram information om fluorkemi och hur tvättprocessen ser ut. Resultatet från intervjuerna har kombinerats med tester på tyger och på ett bärprov med ett byxben med fluorkarbonberedning och ett byxben utan. Bärprovet har testats av en person i dennes dagliga arbete under sex månader. Studien har sammanställt resultatet och kan konstatera att fluorkemin har negativ påverkan på människa och miljö, vilket ligger till grund för en diskussion kring vad som är nödvändig användning. Vidare kan det konstateras att fluorkarbonberedningens effekt försämras över tid, genom användning, tvätt och annan yttre påverkan. Slitaget sker ojämnt och vissa delar av ett plagg kan ha god avvisande effekt medan andra delar är så kallade öppna friytor. Smuts kan då gå in under beredningen och kapslas in. I resultatet har det också framkommit att rätt skötsel av den här typen av plagg är viktigt och att återaktivering genom värme är väsentlig. Samtidigt belyser respondenterna återkommande en mentalitet hos arbetare att de vill att plaggen ska visa att de arbetar och därför vara smutsiga, vilket medför att många plagg sällan tvättas. Genom utförda intervjuer och tester har studien kommit till slutsatsen att fluorkemi inte är nödvändig på varselkläder. Den yttre påverkan som relativt snabb sliter på beredningen genom användning och tvätt i kombination med att fluorkemin inte fyller någon långvarig avvisande funktion är aspekter som tagits i hänsyn för slutsatsen. / Fluor chemistry is used on high visibility workwear to protect the textile from dirt, water, grease, and oil. The chemicals are harmful to people and the environment, they are also very degraded, or they do not break down at all. The chemicals are developed by humans and divided into perfluorinated and polyfluorinated substances (PFAS). PFAS is also classified as PBT substances, which means that they are persistent, bioaccumulate, and toxic. The study was in collaboration with Tranemo Textil AB, where the need for fluorocarbon finish for high visibility workwear was explored. The purpose of the study is to investigate if a fluorocarbon finish is essential on high visibility workwear, based on the use phase and washing process. Through interviews with experts and laundries, the study has obtained information about fluor chemistry and how the washing process works. The results of the interviews have been combined with tests on fabrics and on a wear test that has been tested in the person’s daily work for six months. The wear test is trousers with one leg with fluorocarbon finish and the other leg without. The study has compiled the results and can find that fluor chemistry has a negative impact on humans and the environment, which forms the basis for a discussion about what is essential use. Furthermore, it can be found that the effect of the fluorocarbon finish impairs over time, through use, washing, and other external impacts. The abrasion is uneven, and some parts of the garment can still have a good repellent effect, while other parts have so-called open surfaces. On the open surfaces, dirt can enter during the fluorocarbon finish and be encapsulated. The study has also emerged that proper care of this type of garment is important and that reactivation through heat is essential. At the same time, respondents repeatedly highlight workers' mentality that the garment should show and reflect high work ethics. This causes that many garments are rarely washed and become very dirty. Through interviews and tests, the study has concluded that fluor chemistry is not necessary for high visibility workwear. The external effects with relatively quickly abrasion on the finish through use and washing, this in combination with that fluor chemistry does not fulfil any long-lasting function are aspects that have been considered in the conclusion.

A new approach for predicting octanol-water partition coefficients (Log P) of linear perfluorinated compounds, making use of the limited experimental data available, previous observations and the consistent similarities observed between the experimental and calculated (with electronic structure methods and using EPI suite) slopes of the linear plots of Log P values with the number of carbon atoms (N = 2 to 11) is described here. Eight families of linear organic compounds were investigated: carboxylic acids, perfluorinated carboxylic acids, sulfonic acids and perfluorinated sulfonic acids, together with their corresponding conjugate bases. To the best of our knowledge, this work reports the first application of density functional theory methods to the calculation of Log P values of perfluorinated compounds. A second part of the thesis, describes the study of the thermodynamic stability of the PFOA family of 39 structural isomers with the M06-2X, LC-ωPBE, B97D and B3LYP functionals and with the PM6 method. The PM6 results closely resemble the M06-2X results for neutral PFOAs, but greatly disagree regarding anions. The four functionals applied behave similarly from a qualitative point of view, but quantitatively speaking, the LC-ωPBE and B97D results are between the M06-2X and B3LYP stability results. M06-2X ranks highly substituted isomers as more stable than did B3LYP, and ranks less-branched isomers quite low in relative stability compared to B3LYP. Various similarities with a former PFOSs study applying the M06-2X and B3LYP functionals have been identified. The degree of branching within structural isomers cannot always be precisely determined, and is not the only aspect that determines thermodynamic stability; the pattern of substitution seems to also play a significant role. / Graduate

<div> <p>In recent years, the presence of per- and polyfluoroalkyl substances (PFAS) in aquatic systems has led to research on their fate, effects and treatability. PFAS have been found in various environmental matrices including wastewater effluents, surface, ground, and drinking water. Perfluoroalkyl acids (PFAAs) are the class of PFAS most commonly tested due to their ability to migrate rapidly through groundwater and include perfluoroalkyl sulfonic acids (PFSAs) and perfluoroalkyl carboxylic acids (PFCAs). Of the globally distributed and persistent PFAAs, PFSAs are the most resistant to biological and oxidative chemical attack. This doctoral study focused on a reductive treatment approach with zero valent metals/bimetals nanoparticles (NPs) synthesized onto a carbon material to reduce NP aggregation. Initial work focused on exploring reactivity of different combinations of nano (n) Ni, nFe⁰ and activated carbon (AC) at 22 ^oC to 60 ^oC for transforming perfluorooctanesulfonate (PFOS) from which nNiFe⁰-AC at 60 ^oC led to transformation of both linear (L-) and branched (Br-) PFOS isomers. The remaining research focused on work with nNiFe⁰-AC at 60 ^oC in batch reactors including optimizing nNiFe⁰-AC preparation, quantifying PFOS transformation kinetics and evaluating the effects of PFAA chain length (C4, C6 and C8) and polar head group (PFSA versus PFCA) as well a groundwater matrix on transformation magnitude. Optimization of analytical methods to provide multiple lines of evidence of transformation including fluoride, sulfite and organic product generation was an ongoing throughout the research.</p> <p>nNiFe⁰-AC prepared with a 3-h synthesis stirring time led to the highest PFOS transformation of 51.1 ± 2.1% with generation of ~ 1 mole of sulfite (measured as sulfate) and 12 moles of fluoride. Several poly/per-fluorinated intermediates with single and double bonds were identified using quadrupole time-of-flight mass spectrometry (QToF-MS) in negative electrospray ionization (ESI-) mode with MS/MS fragmentation confirmation as well as one and later two desulfonated products with QToF negative atmospheric pressure chemical ionization (APCI-). All organic transformation products were found in only particle extracts as well as most of the sulfite generated. PFOS transformation kinetics showed that generated fluoride concentrations increased for the first day whereas sulfate concentrations continued to increase during the 5-d reaction. The transformation products identified showed defluorination of single- and double-bond structures, formation of C8 to C4 PFCAs and paraffins from cleavage of the C-S bond.</p> <p>The length of the perfluoroalkyl chain affected the length of time to achieve peak removal, but overall magnitude of transformation when reactions appeared complete were similar for both PFSAs and PFCAs. Like PFOS, PFOA transformation maxed in 1 d whereas shorter chains required more time to reach their peak removal, which is hypothesized to be due to lower sorption of the shorter chain PFAAs to the reactive surfaces. Measured F mass balance was higher for PFOS and PFOA (>90% F) compared to shorter chain PFAAs (~50-70% F). The Perfluorohexanesulfonate (PFHxS) and perfluorobutanesulfonate (PFBS) degradation products include single bond polyfluoroalkyl sulfonates and shorter-chain perfluoroalkyl carboxylates. For example, PFHxS transformation resulted in perfluorohexane carboxylic acid (PFHxA) and perfluorobutane carboxylic acid (PFBA). PFCA transformation products included per- & polyfluoroalkyl carboxylates with single bonds and alcohols with single and double bonds. The effect of inorganic matrix on transformation with nNiFe⁰-AC at 60 ^oC was explored using a contaminated groundwater collected at a former fire-training area in Massachusetts. Transformation appeared ‘generally’ lower than in the single-solute clean water systems, which may have been due to the presence of PFAS precursors that degraded to PFAAs and competitive adsorption between anionic PFAAs and inorganic ions onto the NP surface.</p><p>The research presented here demonstrates that nNiFe⁰-AC at 60 ^oC can mineralize PFAAs even in a typical groundwater matrix. Additional lab and pilot scale studies are needed to clarify the mechanisms leading to transformation as well as why transformation reactions plateau prior to all the parent compounds being transformed. The latter may be due to a poisoning phenomenon that can occur in closed systems, which may not occur in a flowing system more characteristic of an environmental scenario, as well as surface area and reactive site constraints or particle passivation.</p></div>

Arbetet har utförts i samarbete med Naturskyddsföreningen för att undersöka vilka vattenavvisande behandlingar som görs på ytterplagg för barn och hur tillverkarna förhåller sig till perfluorerade ämnen. I arbetet har vattenavvisande ytterplagg för barn i förskoleåldern studerats, med syfte att se i vilken mån perfluorerade ämnen används i plaggen. Barnen som har studerats är utomhus varje dag i alla väder. Vid kraftigt regn eller när det är mycket blött ute används vattentäta regnställ, vid lättare väta bär de ytterplagg med vattenavvisande funktion. En egen oljedropptestmetod har utvecklats. Testet har utförts på de plagg som hänger på förskolorna. Det finns flera typer av vattenavvisande behandlingar. De vanligaste är perfluorerade ämnen, silikoner, dendrimerer och vaxer. De har olika egenskaper och funktioner sinsemellan. De perfluorerade ämnena har den bästa vattenavvisande förmågan och de är också de enda som är oljeavvisande. Perfluorerade ämnen är persistenta, bioackumulerande, hormonstörande och toxiska. Hormonstörande ämnen kan bidra till fetma, cancer, neurologiska störningar, fortplantningsstörningar och missbildningar. Silikoner har goda vattenavvisande egenskaper. Råvaran till silikoner är persistent, bioackumulerande och toxisk. Även dendrimerer har goda vattenavvisande egenskaper. Lite är känt om miljö- och hälsopåverkan men partiklar i nanostorlek kan potentiellt ta sig in cellerna och orsaka cancer. Inga allvarligare miljö- och hälsokonsekvenser av vaxer/paraffiner har hittats. De har sämre vattenavvisande egenskaper, påverkar greppet och tål tvätt och nötning dåligt. De kläder som används på förskolorna håller generellt barnen torra, men en försämring kan märkas på gamla eller dåligt konstruerade plagg. Ytterplagg som behandlats med perfluorerade ämnen är vanliga. Företagen har fasat ut perfluorerade ämnen under de senaste åren, planerar att byta ut dem eller har vidtagit åtgärder enligt Reach. Dendrimerer är det vanligaste alternativet till perfluorerade ämnen. Inga krav förekommer från vare sig företag eller användare på att plaggen ska vara smuts- och oljeavvisande. / Program: Textilingenjörsutbildningen

Perfluoroalkyl substances (PFASs) are anthropogenic compounds that have been classed as persistent organic pollutants (POPs) and are found in both commercial and industrial products. PFASs have been detected in different environmental matrices and have been found to bioaccumulate in all trophic levels. The adverse effects that are associated with PFAS exposure include reduced body weight, increased liver weight, hepatocellular hypertrophy, a decrease in serum cholesterol and triglycerides. This project aims to characterize the metabolic changes in lipid metabolism in the liver after exposure to one of the well-studied PFASs, the perfluorooctane sulfonate (PFOS), during the embryo development using the domestic chicken as a model organism. The characterization of the metabolic changes was done by conducting both quantitative lipidomic analysis and semi-quantitative global profiling on extracted lipids from liver homogenates from a former related project looking at fatty acid profiles. The extracted lipids were analyzed using UHPLC/Q-TOF-MS. In the quantitative analysis, the PFOS-treated groups (0.1 ug/g and 1.0 ug/g)exhibited higher lipid concentrations when compared with the solvent control group (5% DMSO) and the untreated group leading to the conclusion that PFOS exposure disrupts the lipid metabolism. When comparing the lipid concentrations between the two PFOS-treated groups (0.1 ug/g and 1.0 ug/g), the majority of the lipids exhibited higher lipid concentrations in the 1.0 ug/g PFOS-treated groups leading to the conclusion that the effect PFOS has on the lipid metabolism is dose dependent. In the global profiling analysis, 63 lipids showed significant differences when comparing the solvent control group with samples either treated with 0.1 ug/g PFOS or 1.0 ug/g PFOS.

Dietary intake is one of the major routes of human exposure to perfluoroalkyl and/or polyfluoroalkyl substances (PFAS). The objective of this study was to measure perfluorooctane sulfonic acid (PFOS), perfluorooctanoic acid (PFOA) and perfluorohexane sulfonic acid (PFHxS) in organic and conventional egg from Sweden (n=8, consisted of 4 pooled eggs and 4 individuals) and China (n=9, consisted of 4 pooled eggs and 5 individuals) and compare the concentrations of PFAS between the two categories (organic and conventional). Also, to evaluate if there was any difference in concentrations of PFAS between both countries. In the end, evaluation of tolerable weekly intake of PFOS and PFOA due to consumption of egg recommended by the European Food Safety Authority (EFSA) was conducted if consuming these eggs would cause any human health risk. Liquid chromatography-mass spectrometry (LC-MS/MS) was used to analyze PFOS, PFOA and PFHxS in the egg samples. In egg samples from China, PFOA was the predominant PFAS; in an organic egg sample from Shenzhen with concentration up to 2000 pg/g, making up to 86% of the 3 PFAS. In contrast, PFOS had the greatest concentration of all PFAS in egg samples from Sweden and was detected in organic egg sample with concentration up to 184 pg/g, making up to 78% of the 3 PFAS. PFOA in samples from China was 18 times higher compared to egg samples to Sweden; results showed no significant differences in PFAS concentrations in egg samples between Sweden and China. In samples from China, concentrations of PFAS had total mean of 50 pg/g for PFOS, 373 pg/g for PFOA and 13 pg/g for PFHxS. In Sweden, mean concentrations of PFOS, PFOA, and PFHxS were found to be 5, 2, and 1,5 times (respectively) higher in organic eggs when compared to conventional. However, significant difference was only observed for PFOS in Swedish organic eggs (p&lt;0.05, t-7.96, df=6). The different concentrations of contamination between organic and conventional egg could be due to the fish powder in organic chicken feed and ingestion of soil through pecking. The result suggests that current concentrations of PFOS and PFOA in organic and conventional chicken eggs are unlikely to cause any immediate harm to Swedish populations. For Chinese population since the consumption of egg has a high risk of exceeding the TWI, the current concentration of PFOA in organic chicken eggs may cause harm to the population based on TWIs established by EFSA. Further investigation is needed with more samples to be analyzed to confirm this point.

Humans are exposed to persistent organic pollutants (POPs) such as brominated flame retardants (BFRs, specifically polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCD)) and perfluoroalkyl acids (PFAAs, specifically perfluoroalkane sulfonate (PFOS) and perfluorooctanoic acid (PFOA)). They are used in consumer products found in cars, offices, homes and day care centers. Diet was earlier thought to be a major human exposure route for legacy POPs, but does not account for body burdens found for many new POPs and indoor exposure from air and dust has been hypothesized as also important. In this thesis, BFRs in air and dust, and PFAAs in dust from different indoor microenvironments in Sweden were analysed, and the results used to estimate human exposure. BFRs and PFAAs were detected in dust from all microenvironments and PBDEs in all air samples. BFR and PFAA exposure occurs mostly in peoples’ homes with toddlers having higher intakes from dust ingestion than adults. Inhalation and dust ingestion play minor roles compared to diet for humans with median exposures, but in worst case scenarios, dust ingestion may be significant for a small part of the Swedish population. Sampling using home vacuum cleaner bag dust and researcher-collected above floor dust was compared. Correlations were seen for ∑OctaBDE and ∑DecaBDE but not for ∑PentaBDE and HBCD. Higher PBDE concentrations were found in above floor dust but higher HBCD concentrations were found in vacuum cleaner bag dust. BDE-47 concentrations were correlated between vacuum cleaner bag dust and breast milk, indicating exposure through dust ingestion. Similar concentrations of PBDEs were measured in indoor and outgoing air from day care centers, apartment and office buildings. Indoor air explained 54-92% of ∑PentaBDE and 24-86% of BDE-209 total emissions to outdoor air in Sweden, supporting the hypothesis that the indoor environment is polluting ambient air via ventilation systems. / <p>At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 2: Accepted. Paper 3: Accepted. Paper 4: Manuscript.</p>

There is a growing need to develop rapid and cost-effective ecotoxicological tools for risk assessment because traditional methods examine endpoints such as mortality, which do not provide any insight into the mode of action (MOA) of the chemical. Research presented within this thesis illustrates the potential of 1H NMR-based metabolomics as a rapid and routine ecotoxicological tool that can elucidate a chemical’s MOA and also aid in the identification of metabolites of exposure. Metabolomics involves measuring the fluctuations in the endogenous metabolites of an organism within a cell, tissue, bio-fluid or whole organism in response to an external stressor. We focused on the model polycyclic aromatic hydrocarbon (PAH) phenanthrene, and the perfluoroalkyl acids (PFAAs) perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS), due to their recalcitrant nature and widespread prevalence in soil environments. 1H NMR-based metabolomics analysis of the exposure of Eisenia fetida earthworms to sub-lethal phenanthrene exposure via filter paper contact tests revealed a concentration-dependent two-phased MOA: a linear correlation between the metabolic response and exposure concentration at low concentrations followed by a plateau in the responses at high concentrations. Alanine, glutamate, maltose, cholesterol and phosphatidylcholine emerged as potential indicators of phenanthrene exposure. An increased energy demand and an interruption in the conversion of succinate to fumarate in the Krebs cycle were observed due to phenanthrene exposure. Sub-lethal PFOA and PFOS exposure to E. fetida via contact tests for two days revealed heightened responses with higher PFOA and PFOS concentrations. Leucine, arginine, glutamate, maltose, and ATP were identified as potential indicators of PFOA or PFOS exposure. E. fetida responses were then investigated after exposure for two, seven and fourteen days to an artificial soil that was spiked with sub-lethal PFOS concentrations. An exposure time-dependent operation of two separate MOAs were identified. Both the contact tests and artificial soil exposure studies identified an elevation in fatty acid oxidation, a disruption in energy metabolism and biological membrane structure, and also an interruption of ATP synthesis following PFOA and PFOS exposure. This thesis illustrates the promise of NMR-based metabolomics as a routine tool for ecotoxicological assessment of contaminated sites.