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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
11

Method development and screening of extractable organofluorine (EOF) and targeted PFAS analysis in food packaging materials

Larsson, Nora January 2022 (has links)
Per- and polyfluoroalkyl substances (PFAS) have been manufactured and used in differentapplications for several decades, including food packaging materials. During the last 20 yearsthese compounds have been acknowledged as hazardous for humans and the environment, anddifferent regulations on PFAS have been established on both national and international levels.Companies started to phase-out long-chain PFAS, including both PFOA and PFOS, around 20years ago. Since PFAS are persistent, this cause concerns both for our health and theenvironment, as well as possible PFAS contamination in new products due to the recycling ofmaterials. The aim of this study was to find an effective method to extract PFAS from differentfood packaging materials; analyze the samples for their extractable organofluorine (EOF)content using combustion ion chromatography; as well as analyze targeted PFAS in the samplesusing ultra-high performance liquid chromatography tandem mass spectrometry. The findingsof this study suggest that none of the selected samples had EOF contents above the Danishindicator value of 20 mg/kg dw TOF set to determine whether PFAS has been intentionallyadded to a material, and that only two samples exceeded the limit of detection for EOF. Atakeaway bowl made out of 100% sugarcane contained the highest EOF content while the outerpackaging of a cereal box contained the second highest EOF. Both PFOA and PFOS, alongwith other long-chain PFAS were detected in a majority of the samples. The lowest total PFASconcentrations when analyzing for targeted PFAS was detected in the sugarcane take awaybowl. The highest total PFAS concentration was detected in an egg carton, followed by theouter packaging of a cereal box (same as above) and the outer box of a waffle mix. The targetedPFAS was detected in almost all samples, with PFNA and 6:2 diPAP being the most frequentlydetected PFAS. PFCAs, PFSAs, FTSAs, FOSAAs and PAPs were detected in a majority of thesamples. The highest concentrations were measured for diSAmPAP in a majority of thesamples. Mass balance calculations of the sugarcane bowl showed that the targeted PFAS onlyaccounted for 0.04% of the extractable organofluorine content. In conclusion, none of thesamples displayed EOF contents higher than the Danish indicator value, suggesting that noneof the samples were intentionally treated with PFAS. However, targeted PFAS analysis of thesesamples showed that they still contain PFAS, that could be further recycled along with therecycling of paper and board food packaging materials. Considering the persistence of PFASand that these compounds can remain in the recycling chain, with the risk of also being releasedinto the environment, it is of importance that PFAS is not introduced in any of the stages in apaper or board containers life cycle.
12

Déterminants des concentrations sériques de substances per- et polyfluoroalkyliques (PFAS) chez les enfants canadiens

Al Kassem, Hala 05 1900 (has links)
Les déterminants de l’exposition aux substances per- et polyfluoroalkyliques (PFAS) chez les enfants sont mal connus. Cette étude visait à analyser les concentrations sériques de 9 PFAS chez 204 enfants participant à l’étude MIREC-Endo ; évaluer les associations entre ces concentrations et celles dans le sérum maternel (grossesse) et le lait maternel ; évaluer les déterminants des concentrations. Nous avons effectué des statistiques descriptives des concentrations et évalué leurs associations à l’aide de corrélations de Pearson et de tests de comparaisons de moyennes. Des analyses de régression ont été faites pour quantifier l’influence de l’allaitement sur les concentrations sériques. Les moyennes géométriques de PFOS, PFOA, PFHxS, PFNA et PFDA (détectés dans >67% des échantillons) étaient de 1,37 ; 1,21 ; 0,55 ; 0,42 et 0,13 µg/L, respectivement. Les concentrations sériques de certains PFAS étaient corrélées avec les concentrations sériques maternelles (r=0,315 [PFOS], 0,314 [PFOA], 0,328 [PFHxS]) et les concentrations dans le lait (r=0,273 [PFOA], 0,509 [PFHxS], 0,237 [PFNA]). Les concentrations sériques de certains PFAS chez les enfants étaient négativement associées avec l’âge maternel à l’accouchement (PFOS, PFHxS, PFDA), le tabagisme durant la grossesse (PFNA, PFDA), l’emploi de la mère (PFOS), alors qu’elles étaient positivement associées avec le niveau d’éducation maternel (PFNA) et le revenu familial (PFOA). Nous avons observé une augmentation de 2,8% (PFOS) et 1,85% (PFOA) dans les concentrations sériques par mois d’allaitement exclusif. En conclusion, les concentrations sériques de certains PFAS chez les enfants étaient associées aux expositions périnatales, à l’âge de la mère, au revenu familial et à la durée d’allaitement. / The determinants of exposure to per- and polyfluoroalkyl substances (PFAS) in children are unclear. The objectives of this study were to analyze serum concentrations of 9 PFAS in 204 children aged 7.5 to 11.8 years participating in the MIREC-Endo study, to assess associations between these concentrations and those in maternal serum (during pregnancy) and breast milk; and to evaluate the determinants of these concentrations. We performed descriptive statistics of the concentrations and assessed their associations using Pearson correlations and comparison tests. Regression analyses were performed to quantify the influence of breastfeeding on serum concentrations. The geometric means of PFOS, PFOA, PFHxS, PFNA, and PFDA (detected in >67% of samples) were 1.37, 1.21, 0.55, 0.42, and 0.13 µg/L, respectively. Serum concentrations of selected PFASs were correlated with maternal serum concentrations (r=0.315 [PFOS], 0.314 [PFOA], 0.328 [PFHxS]) and milk concentrations (r=0.273 [PFOA], 0.509 [PFHxS], 0.237 [PFNA]). Serum concentrations of children PFAS were negatively associated with maternal age at delivery (PFOS, PFHxS, PFDA), smoking during pregnancy (PFNA, PFDA), maternal employment (PFOS), whereas they were positively associated with maternal education level (PFNA) and family income (PFOA). We observed an increase of 2.8% (PFOS) and 1.85% (PFOA) in serum concentrations per month of exclusive breastfeeding. In conclusion, serum concentrations of selected PFAS in children were associated with perinatal exposures, maternal age, family income, and duration of breastfeeding.
13

Occurrence of Per- and Polyfluoroalkyl Substances (PFAS) in Private Water Supplies in Southwest Virginia

Hohweiler, Kathleen A. 24 May 2023 (has links)
Per- and polyfluoroalkyl substances (PFAS) are a class of man-made contaminants of increasing human health concern due to their resistance to degradation, widespread occurrence in the environment, bioaccumulation in human and animal organ tissue, and potential negative health impacts. Drinking water is suspected to be a primary source of human PFAS exposure, so the US Environmental Protection Agency (US EPA) has set interim and final health advisories for several PFAS species that are applicable to municipal water supplies. However, private drinking water supplies may be uniquely vulnerable to PFAS contamination, as these systems are not subject to EPA regulation and often include limited treatment prior to use for drinking or cooking. The goal of this study was to determine the incidence of PFAS contamination in private drinking water supplies in two counties in Southwest Virginia (Floyd and Roanoke), and to examine the potential for reliance on citizen-science based strategies for sample collection in subsequent broader sampling efforts. Samples for inorganic ions, bacteria, and PFAS analysis were collected on separate occasions by homeowners and experts at the home drinking water point of use (POU) in 10 Roanoke and 10 Floyd County homes for comparison. Experts also collected an outside tap PFAS sample. At least one PFAS compound was detected in 76% of POU samples collected (n=60), with an average total PFAS concentration of 23.5 parts per trillion (ppt). PFOA and PFOS, which are currently included in EPA health advisories, were detected in 13% and 22% of POU samples, respectively. Of the 31 PFAS species targeted, 15 were detected in at least one sample. On average, a single POU sample contained approximately 3 PFAS, and one sample contained as many as 8 different species, indicating that exposure to PFAS in complex mixtures is worth noting. Although there were significant differences in total PFAS concentrations between expert and homeowner collected samples (Wilcoxon, alpha = 0.05), it is unclear whether this difference was due to contamination by the collector or the water usage and time of day of sampling (i.e. morning, afternoon). It is worth noting that there was no significant difference in the number of PFAS species in the samples collected by homeowners and experts. Given the considerable variation in PFAS detections between homes, future studies reliant on homeowner collection of samples appears possible given proper training and instruction to collect at the same time of day (i.e. first thing in the morning). / Master of Science / Per- and polyfluoroalkyl substances (PFAS) belong to a large family of manmade compounds that are commonly used in a variety of household and consumer products due to their unique water and stain resistant properties. PFAS compounds are not easily broken down in the environment and have been detected globally in air, soil, and water samples. In addition to their environmental detections, PFAS are slow to be removed from the body after ingestion and known to cause negative health effects in concentrations less than one part per trillion. Drinking water is considered to a main source of PFAS consumption for humans; as such, the US Environmental Protection Agency (US EPA) has set strict, but not legally binding, interim and final health advisories (HA) for four types of PFAS. However, these health advisories only apply to public water services and do not cover private drinking water systems, such as wells or springs, which are the full responsibility of the well owner. Private drinking water system users often do not treat their water before drinking which may make these systems uniquely vulnerable to PFAS contamination. This study focused on 20 total homes, 10 in Roanoke County and 10 in Floyd County to see if PFAS was present and to determine whether or not homeowners would be able to collect their own samples for PFAS analysis at home as accurately as researchers or experts with proper instructions. Homeowners and experts collected drinking water samples inside at a point of use (POU), usually at a kitchen faucet, and outside of the home, usually from a tap. PFAS were present in 76% (n=60) of POU samples, with an average combined concentration of 23.5 parts per trillion (ppt). The two most well studied PFAS, PFOA and PFOS were detected in 13% and 22% of POU samples, respectively. It was also common to detect at least 3 PFAS in a single sample. Although there were differences in total average concentrations of PFAS in samples collected by homeowners and experts, variation could be caused by several factors indicating that with proper training and instruction it is likely future studies could still rely on homeowners to collect samples for PFAS analysis.
14

Effects of pH and Cation Composition on Sorption of Per- and Polyfluoroalkyl Substances (PFASs) to Soil Particles / Effekter av pH och katjonsammansättning på sorption av per- och polyfluoral- kylsubstanser (PFAS:er) till jordpartiklar

Ullberg, Malin January 2015 (has links)
Per- and polyfluoroalkyl substances (PFASs) have drawn great attention recently, due to their environmental persistence, potential toxicity and global distribution. PFAS is a large family of substances, characterized by a perflourinated carbon chain and a functional group. All PFASs are synthetic and have been widely used since the 1950s due to their unique properties of being both hydrophobic and oleophobic, making them useful for many industries. To be able to predict the fate of PFASs in the environment and to obtain detailed understanding of the transport processes, their partitioning behavior between soil particles and water depending on a range of parameters must be investigated. The aims of this study was to investigate the effects of pH, cation composition, functional group and perfluorocarbon chain length on sorption of PFASs to soil particles, by batch sorption experiment in laboratory scale. The laboratory-scale experiments were combined with modelling of the net charge to evaluate if net charge is a good predictor for sorption of PFASs to soil particles. 14 PFASs of varying length and functional groups were studied (PFBA, PFPeA, PFHxA, PFHpA, PFOA, PFNA, PFDA, PFUnDA, PFDoDA, PFTeDA, PFBS, PFHxS, PFOS and FOSA). The effect on sorption of Na+, Ca2+ (two different concentrations) and Al3+ were investigated at pH-range 3-6. Modelling of net charge was carried out in the geochemical model Visual MINTEQ. The soil had 45% organic carbon content. The adsorption of PFASs was strongly correlated with perfluorocarbon chain length, showing a stronger adsorption to particles with increasing perfluorocarbon chain length (i.e. more hydrophobic). The relation between sorption (represented by the distribution coefficient log Kd) and perfluorocarbon chain length was linear for all PFSAs and C3 to C10 PFCAs. The PFSAs (sulfonate functional group) sorbed stronger to soil particles than the PFCAs (carboxylic functional group), and FOSA (sulfonamide functional group) sorbed the strongest. For most PFCAs, (C5-C13) there was a trend of decreasing log Kd (i.e. decreased sorption) with increasing pH, due to pH-dependent changes of the soil particle surfaces. For short and intermediate perfluorocarbon chain length PFCAs (C5-C8) and for PFHxS among the PFSAs, cations had a clear effect on sorption. Aluminium ions (trivalent, Al(NO3)3) had the largest effect, followed by calcium (divalent, Ca(NO3)2) where higher concentration resulted in stronger sorption. Sodium (univalent, NaNO3) had the least influence on sorption. The net charge modelled with Visual MINTEQ takes into account many parameters (including pH) that affect the surface charge and sorption of PFASs to soil particles. When comparing log Kd for the different PFASs with pH and net negative charge, net charge was a better predictor of sorption of PFASs to soil particles than solution pH alone. / Per- och polyfluoroalkylsubstanser (PFAS:er) har dragit stor uppmärksamhet till sig på senare tid, på grund av deras persistenta egenskaper, potentiella toxicitet och globala utbredning. PFAS är en stor grupp ämnen, kännetecknad av en perflourinerad kolkedja och en funktionell grupp. Alla PFAS är syntetiska och har använts i stor utsträckning sedan 1950-talet på grund av deras unika egenskaper av att vara både vatten- och fettavstötande, vilket gör dem användbara för många industriella tillämpningar. För att kunna förutsäga var dessa föroreningars hamnar i miljön och få mer detaljerad förstående för transportprocesserna, måste deras fördelningbeteende mellan jordpartiklar och vattenundersökas för en rad olika parametrar. Syftet med denna studie var att undersöka effekterna av förändrat pH, katjonsammansättning, funktionell grupp och perfluorkolkedjelängd på sorption av PFAS:er till jordpartiklar. Detta gjordes med sorptionsexperiment i laboratorieskala. Laboratorieexperimentet kompletterades med modellering av nettoladdning, för att se huruvida detta väl kunde förklara sorptionen till jordpartiklar. 14 PFAS:er av varierande längd och med tre olika funktionella grupper studerades (PFBA, PFPeA, PFHxA, PFHpA, PFOA, PFNA, PFDA, PFUnDA, PFDoDA, PFTeDA, PFBS, PFHxS, PFOS och FOSA). Effekten på sorption av Na+, Ca2+ (två olika koncentrationer) och Al3+ undersöktes vid pH-intervallet 3-6. Modellering av nettoladdning utfördes i den geokemiska modellen Visual MINTEQ. Jorden som användes hade en halt av organiskt kol på 45%. Adsorptionen av PFAS:er var starkt positivt korrelerad med kedjelängden på de perfluorinerade kolkedjan. Ju längre kolkedja (dvs. mer hydrofob), desto starkare adsorption till partiklar. Relationen mellan sorptionen (här uttryckt som partitioneringskofficienten log Kd) och kedjelängd var linjär för alla PFSA och för C3 till C10 för PFCA. PFSA (sulfonat) adsorberade starkare än PFCA (karboxyl), och FOSA (sulfonamid) adsorberades starkast. För de flesta PFCA, (C5-C13) fanns en allmän trend där log Kd (dvs. sorption) minskade med ökande pH, på grund av pH-beroende förändringar på jordpartiklarna. För korta och medellånga PFCA (C5-C8) och för PFHxS hade katjonsammansättningen en tydlig effekt på sorptionen. Aluminiumjoner (trevärd, Al(NO3)3) hade den största effekten, följt av kalcium (tvåvärd, Ca(NO3)2) där den högre koncentrationen resulterade i starkare sorption. Natrium (envärd, NaNO3) hade minst påverkan på sorptionen till jordpartiklar. Visual MINTEQ tar hänsyn till många parametrar (inklusive pH), när nettoladdningen på jordpartiklarnas yta räknas ut. När log Kd för olika PFAS:er jämfördes med endera pH eller negativ nettoladdning, drogs slutsatsen att nettoladdning korrelerade bättre med sorption än pH.
15

Toxicity Studies Of Per- and Polyfluoroalkyl Substances (PFAS)

Shittu, Adenike Rofiyat 02 September 2021 (has links)
No description available.
16

PFAS-föroreningar i råvatten. : En studie uppströms Borgs vattenverk / PFAS contamination in raw water. : An upstream study of Borg's water treatment plant

Hansen, Lovisa January 2021 (has links)
Poly- och perfluorerade alkylsubstanser (PFAS) är syntetiskt tillverkade kemikalier som omfattar cirka 4700 individuella ämnen. PFAS har använts sedan 1950-talet i ett antal applikationer som brandsläckningsskum, impregneringsmedel samt textilier, på grund av sina unika egenskaper att vara både vattenlöslig (hydrofila) och vattenavstötande (hydrofoba). Dessa egenskaper gör att göra att PFAS kan transporteras långa vägar. Dessutom är ämnets kol-fluorbindning en av det starkaste kemiska bindningar som gör dem mycket stabila och därför svårnedbrytbara i miljön. Många PFAS misstänkts vara skadliga och kan ansamlas i både djur och människor. Ett antal PFAS har visat sig ge negativa effekter på reproduktion, immunsystem, sköldkörtelhormoner och levern vid djurförsök. Vissa tas lättare upp av kroppen men det är oklart vilken påverkan exakt alla 4700 PFAS-ämnen har. Dessa potentiellt skadliga föroreningar upptäcks på flera ställen i Sverige och har redan resulterat i allvarliga problem för dricksvattenförsörjningen. Dagens reningsmetoder avlägsnar inte PFAS och i kombination med toxiska egenskaper och hög bioackumuleringspotential kan det bli farligt för både människor och miljö. Därför regleras summan av 11 PFAS-ämnen (summa-11) med en åtgärdsgräns på 90 ng/L för vattenverk i Sverige. Vissa vattenverk har tvingats sättas ur bruk på grund av för höga PFAS-koncentrationer i producerat dricksvatten. Kunskapen om källor till PFAS är fortfarande låg men utredning av flera potentiella källor pågår.  I detta arbete har ett antal PFAS-ämnen analyserats uppströms Glan, den sjö i Norrköping kommun som försörjer över 90 % av invånarna med dricksvatten. Syftet är att kartlägga och karaktärisera PFAS i Norrköpings råvattentäkt Glan med tillflöden för att få en ökad förståelse för potentiell påverkan på dricksvattenproduktion. Kartläggningen skedde genom provtagningar uppströms Borgs råvattenintag. Det samlades också in data från andra aktörer längre uppströms i vattensystemet längs Motala Ström, Stångån samt även i Glan. Provtagning skedde också vid Bråvalla som är ett sedan tidigare välkänt förorenat område i direkt anslutning till Glan. All data analyserades sedan med ett Kruskal-Wallis test. Studien visar 1) av 21 analyserade PFAS-ämnen detekterades PFHxS, PFOS, PFPeA, PFHxA, PFHpA, PFOA och PFBA i flest provpunkter 2) Både PFOS och PFOA hade högst koncentration i Motala ström av de tillflöden till Glan som undersökts 3) PFBA, visade högst koncentration i andra tillflöden än Motala Ström, Hällestaån, Ysundaviken, till Glan med okänd källa 4) Av alla inflöden till Glan uppmättes högst halter av summa-11 i Motala ström som också utgör det största tillflödet till Glan 5) Våtmarken vid Bråvalla är en potentiell PFAS-källa till Glan då koncentrationen i dessa provpunkter är mycket höga i jämförelse med övriga provpunkter. Däremot indikerar inte resultaten på att Bråvalla är en källa i dagsläget men kan bidra till framtida komplikationer för Borgs råvattentäkt pga. klimatförändringar. / Per- and polyfluoroalkyl substances (PFAS) are synthetically manufactured chemicals comprising about 4700 individual substances. PFAS has been used since the 1950s in a number of applications such as firefighting foam, impregnating agents and textiles, due to its unique properties of being both water-soluble (hydrophilic) and water-repellent (hydrophobic). These properties allow PFAS to be transported long distances. In addition, the substance's carbon-fluorine bond is one of the strongest chemical bonds that makes them very stable and therefore difficult to degrade in the environment. Many PFASs are suspected to be harmful and can accumulate in both animals and humans. A number of PFASs have been shown to have adverse effects on reproduction, immune systems, thyroid hormones and the liver in animal experiments. Some are more easily absorbed by the body, but it is unclear what effect exactly all 4700 PFAS substances have. These potentially harmful pollutants are discovered in several places in Sweden and have already resulted in serious problems for the drinking water supply. Today's purification methods do not remove PFAS and in combination with toxic properties and high bioaccumulation potential, it can be dangerous for both humans and the environment. Therefore, the sum of 11 PFAS substances (summa-11) is regulated with a limit value of 90 ng/L for waterworks in Sweden. Some waterworks have been forced out of service due to too high PFAS concentrations in produced drinking water. Knowledge of sources for PFAS is still low, but investigation of several potential sources is ongoing. In this study, a number of PFAS substances have been analyzed upstream of Glan, the lake in Norrköping municipality that supplies more than 90% of the inhabitants with drinking water. The aim is to map and characterize PFAS in Norrköping's water catchment Glan with inflows to gain an increased understanding of the potential impact on drinking water production. The mapping took place through sampling upstream of Borg's raw water intake. Data were also collected from other actors further upstream in the water system along Motala Ström, Stångån and also in Glan. Sampling also took place at Bråvalla, which is a previously well-known polluted area in direct connection to Glan. All data were then analyzed with a Kruskal-Wallis test. The study shows 1) of 22 analyzed PFAS substances, PFHxS, PFOS, PFPeA, PFHxA, PFHpA, PFOA and PFBA were detected in most test points 2) Both PFOS and PFOA had the highest concentration in Motala stream of all the inflows examined to Glan 3) PFBA showed the highest concentration in inflows other than Motala stream, Hällestaån, Ysundaviken, to Glan with unknown source 4) Of all inflows to Glan, the highest levels of summa-11 were measured in Motala stream which also constitutes the largest inflow to Glan 5) The wetland at Bråvalla is a potential PFAS source of Glan as the concentration in these test points is very high compared to other test points. However, the results do not indicate that Bråvalla is a source at present, but may contribute to future complications for Borg's raw water source due to climate change.
17

Remediation of per- and polyfluoroalkyl substances (PFAS) in contaminated water by sorption to pine- and spruce bark

Ayranci Dahlberg, Rebecka January 2023 (has links)
PFAS are anthropogenic substances used in many different industrial operations and products because of their unique properties. Due to their negative impact on human health and environmental bioaccumulative characteristics different authorities have addressed the issue. In Sweden the limit is4 ng/L for four different PFAS in drinking water. Another risk to human health is elevated concentrations of toxic elements, causing Sweden to include them in the drinking water regulations withlimits such as 5 µg/L for arsenic, 25 µg/L for chromium and 5 µg/L for lead.This study is a continuation of an investigation for PFAS remediation in contaminated water by sorption to pine and spruce bark. The earlier study was a laboratory scale and implied that pine and spruce have some sorption capacity for long-chain PFAS. In this study pine and spruce bark were used as sorbent at an industrial site. The analysis was performed by weak-anion exchange extraction followed bysupercritical fluid chromatography coupled with a tandem mass spectrometer (SFC-MS/MS) and liquid chromatography coupled with tandem mass spectrometer (LC-MS/MS) for instrumental analyses of target ultra-short-chain PFAS, short- and long chain PFAS and branched PFOS isomers. An elemental analysis was executed with inductively coupled plasma mass spectrometry. The obtained results indicated removal for certain long-chain PFAS, potential for sorption of a specific ultra-short-chain PFAS and the elemental analysis implied some reduction of the chromium concentrations.
18

Electrodialytic Remediation of PFAS-Contaminated Soil

Niarchos, Georgios January 2018 (has links)
Per- and polyfluoroalkyl substances (PFASs) are a group of anthropogenic aliphatic compounds, widelyknown for their environmental persistence and toxicity to living beings. While they are ubiquitous in theenvironment, interest has been focused on contaminated soil, which can act as a primary recipient andsource of groundwater contamination. Electrokinetic technology is based on the movement of ionsunder the effect of an electric field. This could be a promising remediation solution, since PFASs areusually present in their anionic form. The contaminants can then be concentrated towards the anode,thus reducing a plume’s volume and possibly extracting the substances from soil. The preliminary aimof the present study was to evaluate the potential of using electrodialysis for the remediation of PFAScontaminatedsoil for the first time. Experiments were run with natural contaminated soil samples,originating from a fire-fighting training site at Arlanda Airport, and at Kallinge, Sweden, as well as inartificially spikedsoil. Electrodes were placed in electrolyte-filled chambers and separated by the soilwith ion-exchange membranes for pH-control. In total, five experiments were conducted. Two differentsetups were tested, a typical 3-compartment EKR cell and a 2-compartment setup, to allow for pHincrease and facilitate PFAS desorption. Two different current densities were tested; 0.19 mA cm-2 and0.38 mA cm-2. After twenty-one days, soil was cut in ten parts lengthwise and triplicate samples wereanalysed for PFAS concentrations, with HPLC-MS/MS. Sixteen out of the twenty-six screened PFASswere detected above MDL in the natural soil samples. The majority of the detected PFASs showed apositive trend of electromigration towards the anode, under both current densities, with only longerchainedcompounds (c>8) being immobile. This can be attributed to the stronger sorption potential oflong-chained PFAS molecules, as has been reported in previous sorption studies. Mass balancedistribution for a high current density (0.38 mA cm-2) experiment revealed that 73.2% of Σ26PFAS wasconcentrated towards the anode, with 59% at the soil closer to the anode, 5.7% at the anion exchangemembrane and 8.5% at the anolyte. It also showed higher mobility for short-chained molecules (c≤6),as they were the only compounds to be extracted from soil and be concentrated in the anolyte. Highercurrent densities were not directly correlated with higher electromigration rates, as to the lack of massbalance data for the low current density experiments. Regardless, electrodialysis could be a viable optionfor PFAS soil remediation and further research to encourage the understanding of the migrationmechanism, as well as combination with other treatment methods is encouraged. / Per- och polyfluoralkylsubstanser (PFAS) är en grupp av antropogena alifatiska föreningar, allmäntkända för sin miljöpåverkan och toxicitet för levande varelser. Medan de är allestädes närvarande imiljön har intresset varit inriktat på förorenad mark, som kan fungera som primär mottagare och källatill grundvattenförorening. Elektrokinetisk teknik är baserad på jonernas rörelse under effekten av ettelektriskt fält. Detta kan vara en lovande lösningsmedel, eftersom PFAS är vanligtvis närvarande i sinanjoniska form. Föroreningarna kan sedan koncentreras mot anoden, vilket reducerar en plums volymoch eventuellt extraherar ämnena från jorden. Det preliminära målet med den föreliggande studien varatt utvärdera potentialen att använda elektrodialys för sanering av PFAS-förorenad jord för förstagången. Experimenten kördes med naturliga förorenade jordprover, härrörande från enbrandbekämpningsplats vid Arlanda flygplats, och i Kallinge, Sverige, samt i konstgjort spikedsol.Elektroder placerades i elektrolytfyllda kamrar och separerades av jorden med jonbytesmembran förpH-kontroll. Totalt genomfördes fem experiment. Två olika inställningar testades, en typisk 3-facksEKR-cell och en 2-facksinställning, vilket möjliggör pH-ökning och underlättar PFAS-desorption. Tvåolika strömtätheter testades; 0,19 mA cm-2 och 0,38 mA cm-2. Efter tjugo dagar skärs jorden i tio delari längdriktningen och trippelprover analyserades för PFAS-koncentrationer, med HPLC-MS / MS.Sexton av de tjugosex screenade PFAS: erna detekterades över MDL i de naturliga markproverna.Majoriteten av de upptäckta PFAS-värdena visade en positiv trend av elektromigration mot anodenunder båda strömtätheten, varvid endast längre kedjiga föreningar (c> 8) var immobila. Detta kanhänföras till den starkare sorptionspotentialen hos långkedjiga PFAS-molekyler, vilket har rapporteratsi tidigare sorptionsstudier. Massbalansfördelning för ett experiment med hög strömtäthet (0,38 mA cm-2) visade att 73,2% av Σ26PFAS koncentrerades mot anoden, med 59% vid jorden närmare anoden, 5,7%vid anjonbytarmembranet och 8,5% vid anolyten. Det visade också högre rörlighet för kortkedjigamolekyler (c≤6), eftersom de var de enda föreningarna som skulle extraheras från jord och koncentrerasi anolyten. Högre strömtätheter var inte direkt korrelerade med högre elektromigrationshastigheter,avseende bristen på massbalansdata för experimenten med låg strömtäthet. Oavsett elektrodialys kandet vara ett lönsamt alternativ för PFAS-markrening och ytterligare forskning för att uppmuntraförståelsen för migrationsmekanismen, liksom kombinationen med andra behandlingsmetoder främjas.
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Mass flows of per- and polyfluoroalkyl substances (PFASs) in a Swedish wastewater network and treatment plant / Massflöden av per- och polyfluoralkylerade substanser (PFAS) i ett svenskt ledningsnät och reningsverk

Glimstedt, Linda January 2016 (has links)
Per- and polyfluoroalkyl substances (PFASs) are man-made substances that hold unique properties. They are not only oil- and water repellants but also very resistant to degradation. Due to these properties, the applications are endless and PFASs can be found in a wide range of industrial applications and commercial products. The effluents of wastewater treatment plants (WWTPs) have been pointed out as one of the major sources of PFASs in the environment. The main aim of this project was to evaluate the sources and the occurrence of PFASs in a wastewater network in a Swedish city and in the different treatment steps at the connected WWTP. Another objective was to use these data to calculate mass flows and to investigate the fate of PFASs within the WWTP. The city of Uppsala and the WWTP Kungsängsverket were selected as study objects. Both wastewater and sludge were sampled and analyzed. In the wastewater network, a total of 15 pumping stations (PSTs) were sampled for wastewater, and at the WWTP, a total of 10 wastewater and 10 sludge samples were taken. The samples consisted of grab samples (n = 24), time-integrated samples (100 mL every 20 min during 24 hours, n = 2) and flow proportional samples (24 hours, n = 9). The aqueous and sludge samples were prepared for analysis using solid-phase and solid liquid extraction, respectively, and then analyzed by liquid chromatography tandem mass spectrometry (LC/MS/MS). The PFAS concentrations and composition profiles varied greatly in the network. High concentrations of 6:2 fluorotelomer sulfonate (6:2 FTSA) were generally found in the wastewater, which indicates increased usage of 6:2 FTSA in industrial processes and applications as replacement for perfluorooctane sulfonate (PFOS) and/or leaching from fire-training sites. A hot spot was detected (Sågargatan PST: ΣPFAS = 55,000 ng L-1 = 110,000 mg d-1) with elevated discharges of C3 – C8 perfluoroalkyl carboxylates (PFCAs). The studied WWTP was ineffective in removing C4, C6, C8 perfluoroalkyl sulfonates (PFSAs), C3 – C8 PFCAs and 6:2 FTSA from wastewater. Longer chained C9 – C17 PFCAs tended to partition to sludge more effectively than shorter chained C3 – C8 PFCAs, where PFCAs with an even amount of perfluorated carbon atoms had a higher affinity for sludge than those with an odd amount. The PFAS concentrations and mass flows tended to increase across the second clarifier in both wastewater and sludge, probably due to precursor degradation. PFSAs and PFCAs tended to be at similar or lower concentrations in the effluent compared to the influent. This shows that these substances enter the WWTP from an upstream source and are not formed or added in the WWTP. The transformation of precursors is therefore not the most important source of PFASs in Kungsängsverket. PFASs in wastewater at a large scale municipal WWTP may origin to a large extent from both industrial applications and domestic sources, such as daily life products. The new knowledge generated within this project will help Uppsala Vatten to protect drinking water supplies and the receiving aquatic environment from PFAS contamination. / Per- och polyfluoroalkylerade substanser (PFAS) är konstgjorda ämnen som har unika egenskaper. De är inte bara fett- och vattenavvisande utan är även mycket resistenta mot nedbrytning. På grund av dessa egenskaper är applikationerna med PFAS oändliga, och de används i en lång rad industriella applikationer och kommersiella produkter. Renat vatten från avloppsreningsverk har pekats ut som en av de största källorna av PFAS i miljön. Syftet med det här projektet var att undersöka källorna och uppkomsten av PFAS i ett ledningsnät i en svensk stad och även före/efter de olika reningsstegen i det största reningsverket. Ett annat mål var att använda dessa data för att beräkna massflöden och att studera ödet för PFAS i reningsverket. Uppsala stad och reningsverket Kungsängsverket valdes som studieobjekt. Både avloppsvatten och slam provtogs och analyserades. I ledningsnätet provtogs totalt 15 pumpstationer (PST) med avseende på avloppsvatten och i reningsverket togs det totalt 10 avloppsvatten- och 10 slamprover. Proverna bestod av stickprover (n = 24), tidsintegrerade prover (100 mL var 20 min under 24 timmar, n = 2) och flödesproportionerliga prov (24 timmar, n = 9). Vatten- och slamproverna preparerades för analys med hjälp av fastfas- respektive fast-vätske-extraktion, och analyserades därefter med vätskekromatografi kopplat till tandem-mass-spektrometri (LC/MS/MS). PFAS koncentrationerna och sammansättningsprofilerna varierade mycket i ledningsnätet. Koncentrationerna av 6:2 fluorotelomersulfonsyra (6:2 FTSA) var generellt höga i avloppsvattnet, vilket tyder på en ökad användning av 6:2 FTSA i industriella processer och applikationer som ersättningssubstans för perfluorooktansulfonsyra (PFOS) och/eller urlakning från brandövningsplatser. En så kallad hot spot detekterades i ledningsnätet (Sågargatan PST: ΣPFAS = 55 000 ng L-1 = 110 000 mg d-1) med punktutsläpp av C3 – C8 perfluoroalkylerade karboxylsyror (PFCA). Det studerade reningsverket var inte effektivt för rening av C4, C6, C8 perfluoroalkyl-sulfonsyror (PFSAs), C3 – C8 PFCAs och 6:2 FTSA. PFAS av typen C9 – C17 PFCA (långa kolkedjor) tenderade att fördela sig till slamfasen mer än C3 – C8 PFCA (kortare kedjor), där PFCA med ett jämnt antal perfluorerade kolatomer hade större affinitet för slam än de med udda. PFAS koncentrationerna och massflödena tenderade att öka från första till andra sedimentations-tanken, både i avloppsvatten och i slam, troligtvis som en följd av degradering av prekursorer. PFSA och PFCA tenderade att ha likvärdiga eller lägre koncentrationer i ut- jämfört med inflöde. Detta tyder på att huvudkällorna för dessa substanser i avloppsvatten finns uppströms och uppkommer inte genom bildning eller tillsats i reningsverket. Nedbrytning av prekursorer är därför inte den viktigaste källan av PFAS i Kungsängsverket. Det visades tydligt att PFAS i ett kommunalt avloppsvatten kan ha sitt ursprung såväl i både industriella produkter och processer som produkter från hushåll, som t.ex. dagligvaruprodukter. Den nya kunskapen som genererats i detta projekt kommer att hjälpa Uppsala Vatten att skydda dricksvattentäkter och den mottagande akvatiska miljön för PFAS förorening.
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Analysis of Per- and Polyfluoroalkyl Substances (PFASs) in African Darter (Anhinga rufa) Eggs along Vaal River, South Africa : Comparison of Homologue and Isomer Profiles

Fredriksson, Felicia January 2016 (has links)
Per- and polyfluoroalkyl substances (PFASs) are a group of toxic and persistent organic compounds. Their properties make them extremely resistant and they have been shown to have bioaccumulation and toxic properties in the environment and also to biomagnify in both aquatic and terrestrial food webs. This study has analysed different PFASs in African Darter (Anhinga rufa) eggs from five sites along Vaal River; Orange River, South Africa. Sixteen of 23 analysed PFASs were detected and quantified, and the homologue profiles were studied from all five sites. Total perfluorooctane sulfonic acid (PFOS) (all structural isomers) was the predominated compound of all PFASs, accounting for 88-98% for all sites, with a median concentration range of 58 ng/g ww to 2473 ng/g ww. The second highest concentration was found for perfluorodecanoic acid (PFDA) (1.9-42 ng/g ww), followed by perfluorononanoic acid (PFNA) (1.1-14 ng/g ww) and perfluorohexane sulfonate (PFHxS) (0.68-6.0 ng/g ww). The results showed significantly that the three up-stream sites (Welverdiend, Schoemansdrift and Orkney East) had similar patterns and that eggs from Schoemansdrift had the highest levels of PFASs. This may indicate the same source of origin for these three sites and that Schoemansdrift are closest to the contamination source. The three sites (Welverdiend, Schoemansdrift and Orkney East) with similar pattern is closest to Gauteng, which can be where the emission source is located, because it is an industrial area. Perfluoroalkyl carboxylic acids (PFCAs) and PFOS might originate from different sources and the source for PFCAs could be degradation of fluorotelomer-based precursors. Structural isomer profiles of PFOS showed similar results as the PFAS homologue patterns, which give further indication of the source of origin. The contribution of linear PFOS (L-PFOS) to the total amount of PFOS was between the range of 94 and 97%. Bloemhof had the highest concentration of branched isomers among all sites. The L-PFOS concentrations in Bloemhof were also significantly differ from Schoemansdrift. This indicate two different sources between Bloemhof and the three up-steam sites, or an effect of environmental fractionation.

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