The aim with the study was to assess if glacial relict amphipods constitute as vectors of transport of per- and polyfluoroalkyl substances (PFASs) in the Arctic char food web in Lake Vättern, Sweden. Sediment, surface water and biota samples were analysed for PFASs using ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS), and stable isotope analysis of δ 13C and δ15N was performed on sediments and biota samples. Sediment samples (n=3) were suggested to have PFASs originating from different sources. Generally low concentrations were detected in sediment (sum of all detected PFASs were 2.7 ng/g in St. Aspön, 2.9 ng/g in Visingsö and 0.6 ng/g in Omberg, reported in dry weight), compared to biota and several water samples. The PFAS distribution and concentrations in the samples representing St. Aspön and Visingsö deviated from the third sample from Omberg, which was further evidenced by stable isotope analysis. The average concentration of all detected PFASs in the potentially low contaminated samples was 6 ng/L, while it was 5900 ng/L in the potentially aqueous film forming foam (AFFF) contaminated samples. Surface water samples from Jönköping airport and Kärnebäcken measured concentrations of linear perfluorooctane sulfonate (L-PFOS) that all exceeded the Annual Average Environmental Quality Standard (AA-EQS) value of 0.65 ng/L of PFOS in freshwater (fire pond: 14 000 ng/L, ditch: 600 ng/L, Sandserydsån: 160 ng/L, Kärnebäcken: 150 ng/L). A reference sample that was assumed to represent diffuse sources showed similar distribution of PFASs as in several estuaries around Lake Vättern. Since the surface area of Lake Vättern is large (1900 km2), atmospheric deposition is suggested as one of the major contamination sources. This should be further investigated to better assess the local environmental burden. Trophic magnification factors (TMFs) calculated for L-PFOS, perfluorononaoate (PFNA) and perfluorotridecanoate (PFTrDA) were > 1, indicating biomagnification to higher trophic levels. Among all detected PFASs in biota samples, L-PFOS was the most prominent component (58 %), followed by PFTrDA (20 %), PFNA (6.7 %), perfluoroundecanoate (PFUnDA) (5.3 %), perfluorodecanoate (PFDA) (4.9 %) and perfluorooctanoate (PFOA) (2.9 %). Highest concentrations of all targeted compounds (ΣPFAS 220 ng/g) were detected in Monoporeia, the smallest of amphipods. Contamination profiles of perfluorinated carboxylates (PFCAs) showed similar patterns for several species as those derived in another study from Lake Ontario. Mainly Monoporeia and Pallasea, but partly also Mysis are potential vectors of trophic transport of PFASs in Lake Vättern, although further investigations should be conducted including additional replicates and species. Glacial relict crustaceans are sensitive to pollution in a system, and several fish species 3 in the present study had concentrations of L-PFOS above the AA-EQS value of 9.1 ng/g in fish, thus indicating PFAS contamination. Since many fish species feed on glacial relicts, contamination of these amphipods will transfer PFASs further in the Arctic char food web and could thus affect the whole eco-system in Lake Vättern. / Syftet med studien var att undersöka om glacialrelikta amfipoder utgör vektorer för transport av per- och polyfluorerade alkylsubstanser (PFAS)-ämnen i Vätternrödingens näringskedja. Sediment-, ytvatten- och biotaprover analyserades för PFAS-ämnen med ultra-prestanda vätskekromatografi med tandem-masspektrometri (UPLC-MS/MS) samt analys av stabila isotoper av δ 13C och δ15N för sediment- och biotaprover. Sedimentprover (n=3) föreslogs ha PFAS-kontaminering från olika ursprungskällor. Generellt låga halter detekterades i sediment (summan av alla detekterade PFAS-ämnen var 2.7 ng/g i St. Aspön, 2.9 ng/g i Visingsö och 0.6 ng/g i Omberg, rapporterat i torrvikt), jämfört med halterna i biota och flertalet ytvatten. Fördelningen av PFAS-ämnen i proverna från St. Aspön och Visingsö hade liknande homologmönster som skiljde sig från provet från Omberg. Detta styrktes sedan med data från isotopanalys. Medelkoncentrationen av alla detekterade PFAS-ämnen i potentiellt ej filmbildande brandskums (AFFF)-kontaminerade prover var 6 ng/L, medan den var 5 900 ng/L i potentiellt AFFF-kontaminerade prover. I ytvattenprover från Jönköpings flygplats och Kärnebäcken uppmättes halter av linjär perfluoroktansulfonat (L-PFOS) som alla överskred det europeiska gränsvärdet (AA-EQS) på 0,65 ng/L för PFOS i sötvatten (branddammen: 14 000 ng/L, diket: 600 ng/L, Sandserydsån: 160 ng/L, Kärnebäcken: 150 ng/L). Ett referensprov från sjön Unden (liknande ekosystem som Vättern) representerade diffusa utsläppskällor och hade liknande distribution av PFAS-ämnen som ett antal vattendrag i studien. Atmosfärisk deposition är en annan potentiell källa för PFAS-ämnen och då Vätterns ytvattenarea är stor (1900 km2) kan det vara en av de mest bidragande källorna. Detta bör undersökas närmre för att bättre bedöma den lokala miljöpåverkan. Trofiska magnifieringsfaktorer (TMFs) beräknades för L-PFOS, perfluorononansyra (PFNA) och perfluorotridekansyra (PFTrDA) till högre än 1, vilket indikerar biomagnifikation till högre trofiska nivåer. Av alla detekterade PFAS-ämnen i biota var L-PFOS mest förekommande (58 %), följt av PFTrDA (20 %), PFNA (6.7 %), perfluoroundekansyra (PFUnDA) (5.3 %), perfluorodekansyra (PFDA) (4.9 %) och perfluorooktansyra (PFOA) (2.9 %). Högst koncentrationer av alla analyserade ämnen detekterades i vitmärla (Monoporeia), den minsta av amfipoderna. Kontamineringsprofiler av karboxylater visade ett liknande mönster för ett flertal av arterna som även liknande de från en annan studie i sjön Ontario. Främst Vitmärla och taggmärla men delvis pungräka är potentiella vektorer för trofisk transport av PFAS-ämnen i Vättern, även om ytterligare studier med fler replikat och arter bör genomföras. Glacialrelikter är känsliga för förorening och flertalet fiskar analyserade i denna studie uppmätte koncentrationer av 5 L-PFOS över det europeiska gränsvärdet för PFOS i fisk (9,1 ng/g våtvikt), vilket indikerar att Vättern är förorenad. Då många fiskar äter glacialrelikta kräftdjur, skulle kontaminering av dessa amfipoder bidra till biomagnifikation i näringskedjan och således påverka hela Vätterns ekosystem.

Polycyclic aromatic compounds (PACs) are organic compounds that include several sub-groups of toxic, persistent and carcinogenic environmental pollutants consisting of two or more non-substituted or substituted aromatic rings. Due to the complexity of PAC-mixtures found in the environment it can be challenging and time-consuming to track the sources of contamination. In the present study, multivariate data analysis (MVDA) models, such as principal component analysis (PCA) and partial least squares discriminant analysis (PLS-DA) were applied to track sources of PACs at contaminated sites. Based on the chemical profile of 78 PACs obtained in GC-MS analysis of soils, 26 observations were classified according to their petrogenic, pyrogenic or urban background soil origin. Two soil samples of unknown origin collected at a contaminated site in Mjölby, Sweden, were successfully fitted to the validated PLS-DA model and their origins were determined as petrogenic. The study shows that validated PLS-DA models can be applied to predict the petrogenic, pyrogenic and urban background soil origins of samples collected at PAC contaminated sites, thus to track the sources of contamination. It is also concluded that 16 U.S. Environmental Protection Agency’s (EPA) priority polycyclic aromatic hydrocarbons (PAHs) are not sufficient to predict the origin of contamination with PCA or PLS-DA.

No description available.

No description available.

No description available.

No description available.

The aim of this project was to compare two methods for the extraction of perfluoroalkyl substances (PFASs) in water samples. The methods compared were solid phase extraction (SPE) and supramolecular solvents (SUPRAS). Solid phase extraction is a sample preparation process where the desired compound passes through a solid phase and the method uses the affinity for the compound of interest to retain it in the solid phase while the undesired compounds pass through. Supramolecular solvents are an alternative approach for extraction of contaminants, for example PFASs. Supramolecular solvents are liquids that generates from compounds known as amphiphiles. The desired compound is extracted by binding with ionic bond, hydrogen bond, dipole-dipole bond, or other depending on the desired compound. A comparison of methods was evaluated based on method detection limits (MDL), recovery, matrix effects and repeatability. The recoveries for SPE (n=11) were best for short-chain PFASs with recoveries between 81-128%. The recoveries decreased with increasing carbon chain length, probably due to the sorption of analytes to the wall of the container or the reservoir that were not washed thoroughly. The matrix (e.g. surface water) for the solid phase extracted samples were concluded to slightly suppress the signal of most PFASs. The repeatability for the SPE samples had values between 8-59%, with an average of 18%. The recoveries of PFASs (n=4) when using SUPRAS for the extraction of PFASs from water samples were generally lower than those of the SPE method. Especially the short-chain PFASs have poor recoveries in SUPRAS extraction. For longer carbon chain PFASs the recovery for the samples extracted with SUPRAS showed better values (58-135%) but with decreasing chain length the recoveries also decreased. For SUPRAS method to be a feasible option, extraction efficiency of 50-120% would be needed. The matrix effects indicated that the matrix of the SUPRAS extracted samples enhanced the signal of most PFASs. The repeatability could not be calculated for the environmental (SUPRAS Method 1) SUPRAS samples since no replicate blanks were extracted. Spiking experiments on Milli-Q water was performed and had RSD values between 22-85% with a mean value of 39 %. This preliminary test of using SUPRAS as extraction method of PFASs in water need to be further developed. At present SUPRAS is not as efficient for the extraction of PFASs from water as using solid phase extraction. Screening of solvents and possibly salting out need to be tested to increase the efficiency of the extracted compounds.

This thesis is a short review of six papers (Papers 1-6,page 5) concerning studies of enamines from 2-indanones. The unusuallystable 2-(N-pyrrolidyl)indene has been studied (Paper 2 ). As a base catalyst this enamine rearranges 1-methylindene to 3-methylindene with a lower rate constant compared with triethylamine. During this 1 ,3-prototropic rearrangement no hydrogen exchangewas observed (Paper 1). Special attention has been drawn to 1 ,3-rearrangements ofalkyl-substituted enamines of 2-indanone. Prom 1-methyl-2-indanone, which was most conveniently prepared by oxidation of the correspondingindene, a series of enamines has been prepared with varyingamine components. A study of the kinetic control of the formation of these enamines showed that the less substituted double-bondisomer was formed more rapidly than the other form. Furthermore, the nature of the amine group has a significant influence on the composition of the equilibrium mixture observed, but the isomericratios obtained were unexpected in the light of earlier investigationsof enamines from 2-methylcyclohexanone (Paper l). A 13C NMR study of these 2-cycloaminoindenes showed that introduction of a 1-methyl substituent caused a decrease in overlap but the magnitude of this perturbation was almost independent of the variation of the amine component. Furthermore, when using pyrrolidineor hexamethyleneimine as amine parts this decrease in overlapwas of a comparable magnitude with the diminished conjugationnoted in the 3-methyl isomers. However, when piperidine or morpholinewas used the decreased delocalization was more pronounced inthe 3-methyl tautomers compared with the 1-methyl analogues (Paper6). One isomer, 1-methyl-2-(N-piperidyl)indene, has been shown toundergo base- as well as acid-catalyzed 1,3-tautomerizations inpyridine solvent. The isomerization rates using 1,4-diazabicyclo-(2.2.2.)octane or quinuclidine as base catalysts were considerably slower than the rate of the acid-catalyzed reaction or the basecatalyzedrearrangement rates involving alkyl-substituted indenesas substrates. This retarding effect, caused by the amine group, is in agreement with differences in pKA values obtained via simpleHückel calculation (Paper 4). The reaction between pyrrolidine and 1-(2-indanylidene)indan--2-one has been investigated. Two possible mechanisms were sugges-ted for the formation of products consisting of a linear dienamineand an indenyl-substituted enamine (9:1). In the main productisolated by recrystallization, the indenyl substituent was shownto be twisted out of conjugation. This dienamine also underwentacid-catalyzed isomerization to form the enamine product (Paper 3). Convenient syntheses of the pharmacologically interestingN-substituted 2-aminoindanes have also been described. The perchloratesalts of the enamines were treated with sodium borohydride in methanol to afford the desired products (Paper 5). / <p>Diss. (sammanfattning) Umeå : Umeå universitet, 1974</p> / digitalisering@umu

The analytical method of X-Ray Fluorescence has come into quick usage lately with the recent development of hand-held devices that can be taken anywhere. The method can be utilized for quantitative and qualitative analysis of the sample in question. Both methods su er from potential sources of errors that can decrease the accuracy and reliability of the acquired data. This thesis aim to describe the theoretical foundations of some of these issues that can occur in analysis, explaining why the readings from X-Ray Fluorescence (XRF) can di er greatly from the actual value unless proper precautions are taken.

In a cement plant, as in any industry, there are regulations of the level of emissions. One way to reduce the emissions is by decreasing the clinker content in the produced cement by addition of remains from other processes that together with lime produce the same products as pure clinker. The produced clinker varies in reactivity and in a more reactive clinker the addition could be increased, reducing the emissions per tonnage of cement. Today the produced cement is analyzed for strength and the results are then evaluated, which is about 1.5 months after the clinker was produced. Clinker samples from the kiln are analyzed every third hour with X-Ray diffraction to see that the composition is correct. If those samples could be used to predict the strength or heat evolution, parameters could be changed directly to keep a stable clinker production. This would give a more stable product and require less energy to produce, thereby producing less emission. In this study, Florida clinker samples have been mixed with 3.96 % gypsum and ground in a 5kg-mill. The ground cement has been analyzed for sulfur, loss of ignition, free lime, compressive strength and setting time. They have also been analyzed with X-Ray fluorescence, calorimetry and X-Ray diffraction. The results have been correlated with each other two by two to see if any connections could be found. The results of the correlation analysis showed 9 good correlations. No correlation was found between any clinker mineral or module to heat evolution, compressive strength or setting time. Multivariate analysis has also been used but more data is needed for it to be able to predict the cement strength. The calorimetric analyses were performed while developing a method. The method seemed robust and small changes had no large significance although the mixing time could rather be too long since shorter mixing time was not enough.