O presente trabalho apresenta a caracterização química de tintas artísticas brasileiras. Diferente de outras matrizes, os materiais de arte fabricados no Brasil não apresentam informações na literatura que auxiliem em sua conservação e restauração. Amostras de tintas acrílicas e a óleo, nacionais e importadas, foram analisadas pelas técnicas espectroscópicas Raman e infravermelho por transformada de Fourier (FTIR), pirólise acoplada a cromatografia a gás e espectrometria de massas (Py-GC/MS) e microscopia eletrônica de varredura acoplada a espectrometria de fluorescência de raios X (SEM-EDS). Resultados de análise indicam que tintas acrílicas brasileiras são compostas por poliestireno (PS), diferentemente das importadas, compostas por polimetilmetacrilato (PMMA). Enquanto as tintas a óleo apresentam composição semelhante (óleo de linhaça), brasileiras e importadas. Duas pinturas do acervo da Pinacoteca do Estado de São Paulo foram selecionadas para um estudo de caso. As obras apresentam a formação de exsudatos em sua superfície, o que demanda a caracterização química como etapa anterior ao desenvolvimento de uma metodologia de restauração. A obra \"Mandala da saudade\", de Sara Goldman-Belz, é composta por tinta spray (alkyd) e a obra \"Três pessoas\", de Marina Saleme, por tinta a óleo. Os resultados de análise apresentam um primeiro passo no estabelecimento de um banco de dados de materiais artísticos fabricados no Brasil para fins de restauração e perícia criminal de obras de arte. / The current work presents the chemical characterization of Brazilian artistic paints. Differently from other matrices, art materials produced in Brazil lack for information in literature that help in their conservation and restoration. Acrylic and oil paint samples, Brazilian and imported, were analyzed by Raman and Fourier transform infrared (FTIR) spectroscopies, pyrolysis coupled with gas chromatography and mass spectrometry (Py-GC/MS) and scanning electron microscopy coupled with x-ray fluorescence spectrometry (SEM-EDS). Results indicate that Brazilian acrylic paints are composed of polystyrene (PS), differently from imported ones, composed of polymethyl methacrylate (PMMA). Whereas, oil paints present similar composition (linseed oil), Brazilian and imported. Two paintings from the collection of Pinacoteca do Estado de São Paulo were selected for a case study. Both works of art present formation of exudates on their surface, which demands chemical characterization as a previous step to the development of a restoration methodology. The painting \"Mandala da saudade\", by Sara Goldman-Belz, is composed of spray paint (alkyd) and the painting \"Três pessoas\", by Marina Saleme, is composed of oil paint. Results presented in this thesis are the first step towards the establishment of a database for artistic materials produced in Brazil for purposes of art restoration and forensic science.

Cloropropanóis são um grupo conhecido de contaminantes relacionados ao processamento de alimentos. Eles são formados na reação entre lipídeos e cloretos quando submetidos ao tratamento térmico, e podem ser encontrados na forma livre ou ligada. O 3-monocloro-1,2-propanediol (3-MCPD), é classificado pela IARC como possível carcinógeno humano (grupo 2B). O glicidol (e seus ésteres), é classificado também pela IARC como uma substância provavelmente carcinogênica para seres humanos (grupo 2A), e, recentemente, vem sendo encontrado em alimentos. O objetivo deste trabalho foi avaliar a presença do 3-MCPD e do glicidol em óleos vegetais comestíveis utilizando a cromatografia gasosa com detector de massa triplo quadrupolo MS/MS. A técnica utilizada foi a preconizada pela AOCS Cd 29c-13, sendo uma análise indireta, e foi possível adaptá-la visando as determinações do 3-MCPD e glicidol através da construção de curvas de calibração e análises de amostras de referência. O método foi validado e os resultados indicaram o limite de detecção do composto 3-MCPD, de 42,4 µg/kg e o limite de quantificação de 50 µg/kg, e para o Glicidol indicaram o limite de detecção de 43,5 µg/kg e limite de quantificação de 50 µg/kg. Os resultados para 3-MCPD obtidos nos ensaios da curva de calibração e linearidade demonstraram que o método foi capaz de expressar resultados com boa linearidade (0 - 10 mg/kg , r2, = 0.9991). Os resultados obtidos nos ensaios de exatidão obedeceram aos critérios de 70 a 120% de recuperação, e ±20% de variação entre os resultados de acordo com SANTE (2017). O método em questão demonstrou ser seletivo, uma vez que não foram observados picos interferentes nos tempos de retenção dos compostos estudados. Os ensaios de precisão nos níveis baixos, médio e alto e robustez demonstraram que o método é robusto e preciso, portanto a validação foi considerada adequada ao uso pretendido. Foram analisadas 368 amostras de óleos vegetais (76 amostras de óleo de canola, 48 amostras de óleo de milho, 69 amostras de óleo de algodão, 33 amostras de óleo de palma, 10 amostras de óleo de palmiste, 50 amostras de oleína de palma, 30 amostras de óleo de soja e 51 amostras de óleo de girassol). As concentrações das amostras analisadas apresentaram resultados para 3-MCPD com valores médios entre 203 a 1205 µg/kg. Para o Glicidol os valores foram de 2 a 1198 µg/kg, com elevado o desvio padrão entre os resultados analíticos, onde o óleo de palma apresentou a maior variação de 1600 a 5260 µg/kg. Através da avaliação do risco realizada para o composto 3-MCPD foi possível detectar, utilizando o critério do pior cenário de exposição e resultados analíticos, os valores diários de consumo de óleo de algodão de 0,044 µg/kg p.c., de óleo de girassol 0,045 µg/kg p.c., óleo de canola 0,18 µg/kg p.c., óleo de palma de 0,28 µg/p.c, óleo de milho de 0,0462 µg/kg p.c., e o óleo de soja, de maior consumo no Brasil (72%) apresentou o valor de 0,27 µg/kg p.c. O consumo de todos estes óleos, pela a população brasileira, pode ser considerado seguro ao comparar com o valor de TDI Ingestão Diária Tolerável - de 2µg/kg p.c.. Através da avaliação do risco realizada também utilizando o critério de pior cenário de exposição e e resultados analíticos para o composto glicidol foi possível verificar que os valores diários de consumo de óleo de algodão de 0,061 µg/kg p.c., de óleo de girassol 0,03 µg/kg p.c., óleo de canola 0,13 µg/kg p.c. e de óleo de palma de 0,57 µg/p.c, de óleo de milho de 0,11 µg/kg p.c, e o óleo de soja de maior consumo no Brasil (72%) não ultrapassam o valor de 0,288 µg/kg p.c indicando consumo seguro destes óleos para a população brasileira baseado na TDI de 1000µg/kg p.c. / Chloropropanols are a known group of contaminants related to food processing. They are formed during the reaction process between lipids and chlorides when submitted to heat treatment and can be found in free or bound form. The 3-monochloro-1,2-propanediol (3-MCPD), is classified by IARC as a possible human carcinogen (group 2B). Glycidol (and its esters), also classified by IARC as a substance likely to be carcinogenic to humans (group 2A), has recently been found in food. The present study aims to evaluate the presence of 3-MCPD and glycidol in edible vegetable oils using gas chromatography with triple quadrupole MS/MS mass detector. The technique applied is recommended by AOCS, guide Cd 29c-13, an indirect analysis, and allows quantification of 3-MCPD and glycidol by building the calibration curves and analysis of reference samples. The method was validated and the detection limit of the contaminant 3-MCPD of 42,4 µg/kg and the quantification limit of 50 µg/kg was established. For Glycidol the detection limit of was 43,5 µg/kg and quantification limit was 50 µg/kg. The results obtained in the calibration and linearity curves demonstrated that the method could express results with good linearity (0 10 mg/kg, r2, = 0.9991). The results obtained in the trueness trials agreed to the criteria of 70 to 120% of recovery, and ± 20% of variation between the results according to what is preconized by SANTE (2017). The method showed to be selective, since no interfering peaks were observed in the retention times of the studied compounds. The tests performed on low, medium and high values demonstrated the robustness and precision of the method, so the validation was considered completed and suitable for the purpose. A total of 368 vegetable oil samples were analyzed (76 samples of canola oil, 48 samples of corn oil, 69 samples of cottonseed oil, 33 samples of palm oil, 10 samples of kern palm oil, 50 samples of palm olein, 30 samples of soybean oil and 51 samples of sunflower oil). The results found in samples for 3-MCPD were within mean values between 203 and 1205 µg/kg. The results found in samples for glycidol were within mean values between 2 to 1198 µg/kg where palm oil presented the highest variation for glycidol from 1600 to 5260 µg/kg. Through the risk assessment for the contaminant 3-MCPD it was possible to detect the values based on exposed worst case scenario and analytical results. The results for cottom oil were 0,044 µg/kg bw, sunflower 0,045 µg/kg bw, canola 0,18 µg/kg bw and palm oil 0,28 µg/kg bw, corn oil 0,0462 µg/kg bw, and for soybean, which is the most consumed oil in Brazil (72%) the value of 0,27 µg/kg bw. These results indicates safe consumption for these oils based in the Theoretical Daily Ingestion - TDI of 2µg/kg bw. The risk assessment for the glycidol based on exposure worst case scenario and analytical results presented for cottom oil the value of 0,061 µg/kg bw, sunflower 0,03 µg/kg bw, canola oil 0,13 µg/kg bw , palm oil 0,57 µg/kg bw, corn oil 0,11 µg/kg bw and for soybean, which is the most consumed in Brazil - 72% the value of 0,27 µg/kg bw. These results indicates safe consumption for these oils based in the TDI of 1000µg/kg bw.

O presente trabalho apresenta a caracterização química de tintas artísticas brasileiras. Diferente de outras matrizes, os materiais de arte fabricados no Brasil não apresentam informações na literatura que auxiliem em sua conservação e restauração. Amostras de tintas acrílicas e a óleo, nacionais e importadas, foram analisadas pelas técnicas espectroscópicas Raman e infravermelho por transformada de Fourier (FTIR), pirólise acoplada a cromatografia a gás e espectrometria de massas (Py-GC/MS) e microscopia eletrônica de varredura acoplada a espectrometria de fluorescência de raios X (SEM-EDS). Resultados de análise indicam que tintas acrílicas brasileiras são compostas por poliestireno (PS), diferentemente das importadas, compostas por polimetilmetacrilato (PMMA). Enquanto as tintas a óleo apresentam composição semelhante (óleo de linhaça), brasileiras e importadas. Duas pinturas do acervo da Pinacoteca do Estado de São Paulo foram selecionadas para um estudo de caso. As obras apresentam a formação de exsudatos em sua superfície, o que demanda a caracterização química como etapa anterior ao desenvolvimento de uma metodologia de restauração. A obra \"Mandala da saudade\", de Sara Goldman-Belz, é composta por tinta spray (alkyd) e a obra \"Três pessoas\", de Marina Saleme, por tinta a óleo. Os resultados de análise apresentam um primeiro passo no estabelecimento de um banco de dados de materiais artísticos fabricados no Brasil para fins de restauração e perícia criminal de obras de arte. / The current work presents the chemical characterization of Brazilian artistic paints. Differently from other matrices, art materials produced in Brazil lack for information in literature that help in their conservation and restoration. Acrylic and oil paint samples, Brazilian and imported, were analyzed by Raman and Fourier transform infrared (FTIR) spectroscopies, pyrolysis coupled with gas chromatography and mass spectrometry (Py-GC/MS) and scanning electron microscopy coupled with x-ray fluorescence spectrometry (SEM-EDS). Results indicate that Brazilian acrylic paints are composed of polystyrene (PS), differently from imported ones, composed of polymethyl methacrylate (PMMA). Whereas, oil paints present similar composition (linseed oil), Brazilian and imported. Two paintings from the collection of Pinacoteca do Estado de São Paulo were selected for a case study. Both works of art present formation of exudates on their surface, which demands chemical characterization as a previous step to the development of a restoration methodology. The painting \"Mandala da saudade\", by Sara Goldman-Belz, is composed of spray paint (alkyd) and the painting \"Três pessoas\", by Marina Saleme, is composed of oil paint. Results presented in this thesis are the first step towards the establishment of a database for artistic materials produced in Brazil for purposes of art restoration and forensic science.

The sujet de cette these portait sur la caractérisation de la machinerie originale utilisée par les Mimiviridae pour glycosyler les fibrilles entourant leurs capsides en travaillant sur les prototypes des 3 lignées connues, Mimivirus (A), Megavirus chilensis (B) et Moumouvirus australensis (C). Les fibrilles de Mimivirus sont décorées par 2 polysaccharides différents :l’un est caractérisé par la répétition d’un disaccaride linéaire fait de 3)-α-L-Rha-(1→3)-β-D-GlcNAc-(1→, avec un pyruvate branché en position 4,6 du GlcNAc ; l’autre présente une unité répétée branchée de séquence 2)-α-L-Rha-(1→3)-β-D-GlcNAc-(1→ pour le squelette linéaire et du rhamnose branché en position 3 par de 2OMeVioNAc. Nous avons suggéré que les fibrilles de Megavirus sont décorées par plus d'une espèce de polysaccharides/oligosaccharides, donc l’un ayant présentant un trisaccharide de RhaNAc:α-L-4OMe-RhaNAc-(1→3)-α-L-RhaNAc-(1→3)-α-L-RhaNAc-(1→. Les fibrilles de Moumouvirus sont décorées de glucosamine, quinovosamine et bacillosamine. A partir de ces données expérimentales il devenait possible de rechercher de nouveaux gènes responsables de ces glycosylations spécifiques. Le cluster de 9 gènes déjà publié de Mimivirus a pu être étendu à 13 gènes. Un cluster de 14 gènes a été d’autre part identifié dans le génome de Moumouvirus, le premier cluster de gènes de la glycosylation identifié dans la lignée B. Parmi les gènes de glycosylation, l’analyse fonctionnelle in vitro de la protéine L142 a permis de démontrer qu’il s’agit d’une N-acétyltransferase. En conclusion, les fibrilles des Mimiviridae sont lourdement glycosylées and le type de sucres et leur organisation dépend de la lignée considérée. / The aim of this thesis is the study of the innovative glycosylation machinery used by the Mimiviridae family for the glycosylation of the fibrils sourrounding their capsid, using Mimivirus, Moumouvirus australensis and Megavirus chilensis as prototypes of lineages A, B and C, respectively. Mimivirus fibrils are decorated with two distinct polysaccharide: one is characterized by a linear disaccharide repeating unit made of 3)-α-L-Rha-(1→3)-α-D-GlcNAc-(1→, with a pyruvic acid branched at position 4,6 of GlcNAc.; the other has a branched repeating unit with the sequence 2)-α-L-Rha-(1→3)-β-D-GlcNAc-(1→ in the linear backbone and rhamnose further branched at position 3 by viosamine methylated at position 2 and acetylated at position 4. We suggested that Megavirus chiliensis fibrils are decorated by more than one polysaccharides/oligosaccharide species, one having this trisaccharide: α-L-4OMe-RhaNAc-(1→3)-α-L-RhaNAc-(1→3)-α-L-RhaNAc-(1→. Moumouvirus australensis fibrils are decorated with glucosamine and quinovosamine in addition to the rare sugar, bacillosamine. Starting from this experimental data, it was possible to identify new genes involved in glycosylation. As a result, the published nine-gene cluster of Mimivirus was extended to thirteen genes. A different cluster of fourteen genes was identified in Moumouvirus australensis, representing the first glycosylation gene cluster identified for the B lineage.Among the glycosylation genes, the function of L142 was investigated in vitro, demonstrating that it is an N-acetyltransferase. To conclude, the fibrils of Mimiviridae are heavily glycosylated and the type of sugars and their organization depends on their lineage.

<p>På SSAB i Borlänge har man upptäckt att avgaser från färgen förorenar ugnarna vid härdning. Avgaserna består av lösningsmedel och andra flyktiga föreningar som sedan förkolnas och faller ner på lackerade plåtband. För att komma runt det här problemet har SSAB tillsammans med Akzo Nobel Industrial Finishes AB, i Gamleby, tillverkat en färg som inte ska ge ifrån sig något lösningsmedel och på så sätt minska bildandet av föroreningar i ugnarna. Färgen heter NOVA GreenCoat och innehåller rapsmetylester, RME, som är ett reaktivt lösningsmedel och ska binda till bindemedlet i färgen och på så sätt hindras från att avgå vid härdning.</p><p>Syftet har varit att undersöka om en viss metod fungerar bra för att samla upp avgaser vid härdning. Avgaserna analyserades med GC-MS och härdningen studerades med FTIR. Arbetet har utförts både i Borlänge och i Gamleby.</p><p>Metoden för uppsamling av avgaserna visade sig fungera, dock inte särskilt effektivt. Den skulle därför behöva optimeras.</p><p>Härdningen kunde till viss del följas med hjälp av FTIR. Förändring i IR-spektrumet syntes för hydroxyltoppen vid cirka 3500 cm^-1. En skillnad kunde ses för en topp vid 2858 cm^-1 som uppkom i det ohärdade materialet innehållande RME, men den försvann under härdning. Toppen ökade med ökad mängd RME och syntes inte alls för de prover som inte innehöll RME.</p><p>Samtliga gjorda analyser indikerade att RME avgick vid härdning. Vid analys med GC-MS kunde de föreningar som avgick från RME identifieras som: metyl-14-metyl pentadekanoat och/eller metyl hexadekanoat, olika former av metyl oktadekanoat samt olika former av metyl eikosanoat. Andra föreningar från klarlacken som avgick var lösningsmedel x och y samt i två av proverna hexametoximetylmelamin, HMMM.</p> / <p>Problems with exhaust gases from paint that contaminates the ovens have been discovered at SSAB in Borlänge.  The exhaust gases contain solvents and other volatiles that vaporize from the paint and later on carbonize and fall down on the next coming sheets. SSAB and Akzo Nobel Industrial Finishes AB have developed a paint that is not supposed to vaporize any solvents and therefore reduce the contaminations of the ovens. The paint is called NOVA GreenCoat and contains rapeseed methyl ester, RME. RME is a reactive solvent that is supposed to react with the binder in the paint and therefore be prevented from leaving during thermal cure.</p><p>The purpose was to investigate whether a specific method worked well, for collecting the exhaust gases during thermal cure, or not. The collected exhaust gases were analyzed by using GC-MS and the cure was studied with FTIR. The work was executed both in Borlänge and Gamleby.</p><p>The method for collecting the exhaust gases worked, unfortunately it wasn’t particularly effective. It therefore needs to be optimized.</p><p>The cure could partially be studied by using FTIR. Changes in the IR-spectrum could be followed by looking at the hydroxyl peak at approximately 3500 cm^-1. A certain difference was observed for a peak at 2858 cm^-1 that appeared in the uncured material containing RME. The peak disappeared during cure. It increased with increased amount of RME and could not be observed at all for the samples that did not contain RME.</p><p>All the analyzed samples indicated that RME vaporize during cure. When analyzed with GC-MS the volatiles that vaporize from RME were identified as: hexadecanoic acid methyl ester and/or penta decanoic acid methyl-14-methyl ester, different forms of octadecanoic acid methyl ester and different forms of eicosanoic acid methyl ester. Other volatiles that vaporize from NOVA GreenCoat were solvent x and solvent y and for two of the samples hexa metoxy methyl melamine, HMMM, was also found.</p>

På SSAB i Borlänge har man upptäckt att avgaser från färgen förorenar ugnarna vid härdning. Avgaserna består av lösningsmedel och andra flyktiga föreningar som sedan förkolnas och faller ner på lackerade plåtband. För att komma runt det här problemet har SSAB tillsammans med Akzo Nobel Industrial Finishes AB, i Gamleby, tillverkat en färg som inte ska ge ifrån sig något lösningsmedel och på så sätt minska bildandet av föroreningar i ugnarna. Färgen heter NOVA GreenCoat och innehåller rapsmetylester, RME, som är ett reaktivt lösningsmedel och ska binda till bindemedlet i färgen och på så sätt hindras från att avgå vid härdning. Syftet har varit att undersöka om en viss metod fungerar bra för att samla upp avgaser vid härdning. Avgaserna analyserades med GC-MS och härdningen studerades med FTIR. Arbetet har utförts både i Borlänge och i Gamleby. Metoden för uppsamling av avgaserna visade sig fungera, dock inte särskilt effektivt. Den skulle därför behöva optimeras. Härdningen kunde till viss del följas med hjälp av FTIR. Förändring i IR-spektrumet syntes för hydroxyltoppen vid cirka 3500 cm-1. En skillnad kunde ses för en topp vid 2858 cm-1 som uppkom i det ohärdade materialet innehållande RME, men den försvann under härdning. Toppen ökade med ökad mängd RME och syntes inte alls för de prover som inte innehöll RME. Samtliga gjorda analyser indikerade att RME avgick vid härdning. Vid analys med GC-MS kunde de föreningar som avgick från RME identifieras som: metyl-14-metyl pentadekanoat och/eller metyl hexadekanoat, olika former av metyl oktadekanoat samt olika former av metyl eikosanoat. Andra föreningar från klarlacken som avgick var lösningsmedel x och y samt i två av proverna hexametoximetylmelamin, HMMM. / Problems with exhaust gases from paint that contaminates the ovens have been discovered at SSAB in Borlänge.  The exhaust gases contain solvents and other volatiles that vaporize from the paint and later on carbonize and fall down on the next coming sheets. SSAB and Akzo Nobel Industrial Finishes AB have developed a paint that is not supposed to vaporize any solvents and therefore reduce the contaminations of the ovens. The paint is called NOVA GreenCoat and contains rapeseed methyl ester, RME. RME is a reactive solvent that is supposed to react with the binder in the paint and therefore be prevented from leaving during thermal cure. The purpose was to investigate whether a specific method worked well, for collecting the exhaust gases during thermal cure, or not. The collected exhaust gases were analyzed by using GC-MS and the cure was studied with FTIR. The work was executed both in Borlänge and Gamleby. The method for collecting the exhaust gases worked, unfortunately it wasn’t particularly effective. It therefore needs to be optimized. The cure could partially be studied by using FTIR. Changes in the IR-spectrum could be followed by looking at the hydroxyl peak at approximately 3500 cm-1. A certain difference was observed for a peak at 2858 cm-1 that appeared in the uncured material containing RME. The peak disappeared during cure. It increased with increased amount of RME and could not be observed at all for the samples that did not contain RME. All the analyzed samples indicated that RME vaporize during cure. When analyzed with GC-MS the volatiles that vaporize from RME were identified as: hexadecanoic acid methyl ester and/or penta decanoic acid methyl-14-methyl ester, different forms of octadecanoic acid methyl ester and different forms of eicosanoic acid methyl ester. Other volatiles that vaporize from NOVA GreenCoat were solvent x and solvent y and for two of the samples hexa metoxy methyl melamine, HMMM, was also found.

This thesis has been performed at Clinical Chemistry at Sahlgrenska University Hospital in Gothenburg. The purpose of the project was to investigate new and alternative ways to determinate synthetic cannabinoids by gas chromatography-mass spectrometry. Currently, the possibilities to quantify synthetic cannabinoids are very limited. This can lead to an increased use of synthetic cannabinoids as the risk of detection is low, which may be known by drug users. The synthetic cannabinoids are sold mixed with different herbs and have varying names like Spice Gold, Spice Silver, K2, Smoke and Pot-pourri. The synthetic cannabinoids analyzed were JWH-018 and JWH-073, which are commonly found in seized Spice material. At intake of these drugs, usually through smoking, cannabis-like effects arise. This is because they bind to cannabinoid receptors in a similar way as THC does, which is the primary active cannabinoid of cannabis. For urine samples an analytical method would probably be the most sensitive if the major metabolite could be analyzed, as it is expected to be present in high concentrations in this sample type. Since information regarding the metabolism of synthetic cannabinoids is very limited there may be reasons to analyze the mother substance in urine. Further, in plasma and serum samples the mother substance is expected in high concentrations. Thus different ways to detect JWH-018 and JWH-073 directly were investigated in this project. Derivatization of JWH-018 and JWH-073 was the first step to get more selective and sensitive GC-MS analysis. Different derivatization-reagents were investigated, for example BSTFA and TFAA. The results show that the derivatization of JWH-018 with BSTFA after reduction and extraction was successful. To achieve this, samples had to be heated at 115°C for 1-3 hours, but still the samples were not completely derivatized. The results indicate that JWH-substances are difficult to derivatized, but they are possible to derivatize with BSTFA. This could mean that a GC-MS-method maybe could be established for these substances, preferably trough TFAA-derivatization.

Analysis of organic residue absorbed in to the walls of ceramic vessels has proved to be a valuable contributor to the knowledge of prehistoric societies. Based on the analysis of absorbed lipids in the wall of ceramic vessels and existing knowledge and theories about the Pitted Ware culture, an attempt of understanding of the Pitted Ware site Vendel is made. Based on the obtained results and evidences presented throughout the paper it is argued that the Vendel site is a permanent or seasonal settlement, and furthermore that the results seem to reflect a change in vessel use towards the end of the Pitted Ware Culture, and possibly even a change of society, ideology and economy.

Einige der Polyzyklischen Aromatischen Kohlenwasserstoffe (PAK) weisen Krebs auslösende Eigenschaften auf. Die bekannteste karzinogene PAK-Verbindung ist das Benzo[a]pyren (BaP), welches bislang als Leitsubstanz verwendet wird. Mittlerweile bestehen jedoch Zweifel, ob BaP als alleinige Leitsubstanz geeignet ist. Daher empfiehlt die EU-Kommission die Untersuchung der PAK auf die so genannten 16 EFSA-PAK auszudehnen. Zur Überprüfung der Anwendbarkeit von BaP als Leitsubstanz war es notwendig, Erkenntnisse über das Verhältnis des Gehaltes an BaP zum PAKges-Gehalt sowie die einzelnen PAK-Profile zu gewinnen. Die zu untersuchenden Lebensmittelgruppen wurden eingeschränkt auf Fleischerzeugnisse, Rauchwürzer und Räuchersalze, Räucherdärme, Gewürze, Tee und Schokolade. Nach der Entwicklung und Überprüfung von Methoden zur Bestimmung der EFSA-PAK und der anschließenden Analytik einer Anzahl repräsentativer Proben verschiedener Lebensmittelgruppen konnte mit Hilfe einer Datensammlung zu den Gehalten der 16 EFSA-PAK die Beurteilung von BaP als Leitsubstanz erfolgen. Es konnte eine Abhängigkeit der PAKges-Gehalte vom BaP-Gehalt ermittelt werden, welche sich mit zunehmender Konzentration der PAK manifestierte. Aus analytischer Sicht eignet sich BaP am besten als Leitsubstanz, da sie chromatographisch mit den heutigen Methoden leicht von anderen möglichen coeluierenden Substanzen abgetrennt werden kann und in Konzentrationen vorkommt, die zuverlässiger quantifiziert werden können.

Massiver wirtschaftlicher Schaden und der Verlust des Verbrauchervertrauens hervorgerufen durch die BSE - Krise führten zu einer radikalen Änderung in der Futtermittel- und Lebensmittelgesetzgebung. Neben diversen anderen Maßnahmen wurden u. a. das Gehirn und Rückenmark von über 12 Monate alten Wiederkäuern vom Gesetzgeber als so genanntes spezifiziertes Risikomaterialien (SRM) definiert. Die spezielle Entsorgung und das Verarbeitungsverbot dieser Materialien in Lebens- und Futtermitteln hatte zum Ziel die Infektkette zu unterbrechen und dadurch das Risiko einer Infektion mit dem BSE-Erreger für den Verbraucher zu senken. Um die Einhaltung des Verarbeitungsverbotes von SRM in Lebensmitteln zu überprüfen, wurden diverse ZNS-Nachweisverfahren entwickelt. Jedoch ist keines, der hierfür entwickelten molekularbiologischen und immunochemischen Verfahren in der Lage sowohl Spezies, als auch Tieralter des nachgewiesenen ZNS zu bestimmen und damit eine potentielle Einordnung zum SRM zu ermöglichen. Darüber hinaus hat sich für fast alle ZNS-Marker der Einfluss von hohen Prozesstemperaturen als nachteilig für die Nachweisbarkeit erwiesen. NIEDERER und BOLLHALDER (2001) entwickelten ein auf Fettsäureanalytik basierendes ZNS-Nachweisverfahren, welches am Institut für Lebensmittelhygiene der Universität Leipzig weiterentwickelt wurde. Vorteile dieses Verfahrens sind die hitzestabilen Marker und die Möglichkeit mit Hilfe von spezifischen Fettsäureverhältnissen Spezies und Tieralters des nachgewiesenen ZNS zu ermitteln. Somit ist es mit diesem Verfahren erstmals möglich das nachgewiesene ZNS der Gruppe der spezifizierten Risikomaterialien zuzuordnen. Ziel dieser Arbeit war es, das am Institut für Lebensmittelhygiene weiterentwickelte Verfahren auf Praxistauglichkeit anhand eines externen Blindversuchs zu testen. Hierbei sollten mögliche Schwachstellen identifiziert und im weiterführenden Verlauf dieser Arbeit Lösungen erarbeitet werden. Für den Blindversuch wurden vom Max-Rubner-Institut, Standort Kulmbach, insgesamt 72 Brühwurstproben zur Verfügung gestellt, welche mittels des nach LÜCKER et al. (2005) beschriebenen Verfahrens untersucht wurden. Die Ergebnisse des Blindversuchs deuten auf eine grundsätzliche Eignung des Verfahrens für den Nachweis von spezifiziertem Risikomaterial in Fleischerzeugnissen hin. Jedoch konnte bei der Tierartdifferenzierung und vor allem bei der Altersbestimmung ein Optimierungsbedarf ermittelt werden. Somit ergaben sich für diese Arbeit folgende weiterführende Aufgabenstellungen: 1. Die Optimierung der Tierartbestimmung auch im Hinblick auf Erweiterung des Speziesspektrums und 2. die Optimierung der Tieraltersbestimmung von Rinder- und Schaf-ZNS. Insgesamt 257 ZNS-Proben der Spezies Rind, Schaf, Schwein, Ziege und Geflügel wurden einer Fettsäureanalyse unterzogen. Aus allen analysierten Fettsäuren wurden 67 Fettsäureverhältnisse gebildet. Zur Identifikation für die Speziesdifferenzierung geeigneter Fettsäureverhältnisse wurde das statistische Verfahren der Partial Least Square – Discriminant Analysis (PLS-DA) eingesetzt. Hierbei ergab sich, dass von den 67 untersuchten Fettsäureverhältnissen insgesamt 14 für die Differenzierung zwischen den Tierarten Rind, Schwein, Schaf, Ziege und Geflügel geeignet sind. Für die Optimierung der Tieraltersbestimmung wurden 37 ZNS-Proben vom Rind und elf ZNS-Proben vom Schaf untersucht. Die analysierten Fettsäuren wurden auf ihre Korrelation mit dem Alter untersucht. Stark korrelierende Fettsäuren und deren Verhältnisse wurden mit Hilfe der Regressionsanalyse auf ihre Vorhersagefähigkeit geprüft. Hierbei gelang die Identifikation von vier neuen Fettsäureverhältnissen. Für die Altersschätzung bei der Tierart Rind scheinen sich die FS-Verhältnisse 2OH-C24:0/2OH-C25:0 und 2OH-C24:1(n-7)/2OH-C25:0 am besten zu eignen. Für die Tierart Schaf sollten die Verhältnisse 2OH-C25:0/2OH-C26:0 und 2OH-C25:0/2OH-C26:1(n-7) bevorzugt eingesetzt werden. Im Vergleich zur bisherigen Verfahrensweise ist mit Hilfe dieser Fettsäureverhältnisse und deren Regressionsformeln eine deutlich präzisere Altersschätzung für die Tierarten Rind und Schaf möglich. Der neue Ansatz bietet die Möglichkeit flexibel auf zukünftige Änderungen der Altersgrenze von SRM zu reagieren. / The immense economical damage and the loss of consumer trust caused by the bovine spongiform encephalopathy (BSE) - crisis resulted in a radical alteration of the feed- and foodlegislation. Besides several other measures, the legislator defined the brain and spinal cord of ruminants older than 12 month as specified risk material (SRM). The special disposal and the processing prohibition of these materials in food and feedstuffs aimed to interrupt the infection chain and to reduce the risk of an infection caused by the BSE pathogen for the consumer. In order to control the processing prohibition of SRM in food, several CNS detection methods were developed. But none of the designed molecular biological or immuno chemical methods has the ability to detect species and age of the CNS. Therefore, a classification of the detected CNS as SRM is not possible. Furthermore, high process temperatures influence nega-tively the detection of almost all CNS markers. NIEDERER and BOLLHALDER (2001) developed a CNS detection procedure based on the analysis of fatty acids, which was improved at the Institute of Food Hygiene, University Leipzig. Advantages of this procedure are the heat stability of the markers and the possibility to identify species and age of the detected CNS. Therefore, this procedure is the first, which facilitates the potential of identifying SRM. The aim of this work was to test the practicability of the improved CNS detection procedure in an external blind trial. During this, possible weak points should be identified and solutions for their elimination presented. Furthermore, the sample preparation of the method should be optimized with regard to cost and time reduction. For the external blind trial the Max-Rubner-Institute, Kulmbach, produced 72 emulsion type sausages. These sausages were analysed according to the procedure described by LÜCKER et al. 2005. The results of the blind trial show the suitability of the procedure for the detection of SRM in meat products in principle. However, some results revealed that the species and age identification required further enhancement. Therefore, the following additional topics of this work were: 1. Optimization of species identification especially with regard to other species 2. Optimization of animal age prediction for cattle and sheep CNS. Selected fatty acids of total 257 CNS samples from cattle, pig, sheep, goat and several poultry species were analysed. These fatty acids were combined to 67 fatty acid ratios. Afterwards, the application of these ratios for the species detection was tested by using the statistical method of Partial Least Square – Discriminant Analysis (PLS-DA). In result, 14 out of 67 fatty acid ratios are suitable for differentiation between the species cattle, pig, sheep, goat and poultry. For the optimization of animal age prediction 37 CNS samples from cattle and eleven CNS samples from sheep were examined. All analyzed fatty acids were checked for their correlation with age. Afterwards strong correlating fatty acids and their fatty acid ratios were examined for their predictive ability by the application of regression analysis. In result, four new fatty acid ratios for age prediction could be identified. For the age prediction of cattle CNS the fatty acid ratios 2OH-C24:0/2OH-C25:0 and 2OH-C24:1(n-7)/2OH-C25:0 are the best choice. In sheep CNS the ratios 2OH-C25:0/2OH-C26:0 and 2OH-C25:0/2OH-C26:1(n-7) should be preferred for prediction of age. In comparison to the previous age prediction method, the application of these fatty acid ratios and their regression formula led to more accurate results. Furthermore, it offers the possibility to adopt to possible variations of the age limits within the SRM definition in future.