19 Dec 2004. / Published through the Information Bridge: DOE Scientific and Technical Information. "IS-T 1930" Heather Marie Netzloff. 12/19/2004. Report is also available in paper and microfiche from NTIS.

Thesis (Ph.D.); Submitted to Iowa State Univ., Ames, IA (US); 19 Dec 2004. / Published through the Information Bridge: DOE Scientific and Technical Information. "IS-T 2134" Meera Jay Desai. US Department of Energy 12/19/2004. Report is also available in paper and microfiche from NTIS.

Η διφωτονική απορρόφηση (ΔΦΑ) είναι το μη γραμμικό-φαινόμενο κατά το οποίο δύο φωτόνια απορροφούνται ταυτόχρονα σε ένα υλικό μέσο. Τα τελευταία 20 χρόνια το φαινόμενο αυτό έχει προσελκύσει ιδιαίτερα το ενδιαφέρον της επιστημονικής κοινότητας για την ανακάλυψη νέων αποδοτικών ενώσεων λόγω και των εφαρμογών που έχει βρεθεί ότι μπορεί να προσφέρει. Η διφωτονική μικροσκοπία, ο διφωτονικός πολυμερισμός, η τρισδιάστατη αποθήκευση δεδομένων είναι μερικές από τις σημαντικές εφαρμογές που εκμεταλλεύονται τα πλεονεκτήματα της ΔΦΑ. Τη τελευταία δεκαετία η έρευνα επικεντρώνεται στη θεωρητική και πειραματική μελέτη της ΔΦΑ οργανικών ενώσεων με σκοπό την διασύνδεσης των χαρακτηριστικών της δομής των μορίων με την ΔΦΑ που παρέχουν και την εύρεση στρατηγικών σύνθεσης οργανικών ενώσεων υψηλής ΔΦΑ. Επίσης πολλές είναι οι επιστημονικές εργασίες που χρησιμοποιούν τις ενώσεις αυτές στην έρευνα για την ανάπτυξη και βελτίωση των διφωτονικών εφαρμογών. Στη διατριβή αυτή γίνεται μελέτη της ΔΦΑ συζυγιακών οργανικών ενώσεων αποτελούμενες από ένα κεντρικό τμήμα συνδεδεμένο αντιδιαμετρικά με δυο ίδιους υποκαταστάτες. Τα συμμετρικά αυτά μόρια έχουν ως κεντρικό τμήμα φλουορένιο ή αλκόξυ-φαινυλένιο ή καρβοξύλιο και διάφορους υποκαταστάτες στα άκρα. Η τεχνική μέτρησης διφωτονικά διεγερμένου φθορισμού με laser femtosecond χρησιμοποιήθηκε για τον υπολογισμό των τιμών της ενεργούς διατομής ΔΦΑ των μορίων στη φασματική περιοχή 750-840nm. Από τη συγκριτική μελέτη των ενώσεων προκύπτει ότι ο υποκαταστάτης φθαλιμίδιο προσφέρει την μεγαλύτερη ΔΦΑ και για τα τρία διαφορετικά κεντρικά τμήματα, ενώ όταν συνδέεται με το φλουορένιο έχει την υψηλότερη ενεργό διατομή ΔΦΑ φθάνοντας την τιμή των 1650GM στη φασματική περιοχή που μελετήθηκε. Επίσης παρατηρήθηκε ότι ο υποκαταστάτης ναφθαλιμίδιο προκαλεί μετατόπιση του μεγίστου ΔΦΑ σε αρκετά μεγαλύτερα μήκη κύματος. Παρόμοια μετατόπιση παρατηρείται και για τα μόρια με κεντρικό τμήμα το καρβαζόλιο. Η μετατόπιση αυτή του φάσματος ΔΦΑ δεν αντιστοιχεί σε μετατόπιση του φάσματος μονοφωτονικής απορρόφησης. Οφείλεται στην άρση της κεντροσυμμετρίας του μορίου, λόγω της διαμόρφωσης της δομής του, η οποία κάνει επιτρεπτή τη διφωτονική μετάβαση στην πρώτη μονοφωτονικά επιτρεπτή ενεργειακή κατάσταση που ειδάλλως είναι απαγορευμένη. Η επίδραση του διαλύτη στις διφωτονικές ιδιότητες των μορίων μελετάται επίσης στη διατριβή αυτή. Για τις τέσσερις πιο αποδοτικές ενώσεις, ως προς το διφωτονικά διεγερμένο φθορισμό, έγιναν μετρήσεις για τον υπολογισμό των φασμάτων ΔΦΑ τους σε πέντε διαλύτες διαφορετικής πολικότητας (διηλεκτρικής σταθεράς). Από τις μετρήσεις φάνηκε η σημαντική επίδραση του διαλύτη στη ΔΦΑ των τεσσάρων χρωστικών η οποία μεγιστοποιείται σε διαλύτη μεσαίας πολικότητας, ο τρεις στην ακετοφαινόνη και μια στο THF. Η χαμηλή κβαντική απόδοση φθορισμού που παρατηρείται στα διαλύματα με ακετοφαινόνης μειώνει αρκετά το διφωτονικά προκαλούμενο φθορισμό και κατατάσσει τo THF ως τον αποδοτικότερο διαλύτη για διφωτονικές εφαρμογές που εκμεταλλεύονται το φθορισμό. Επίσης και ο μη πολικός διαλύτης τολουόλιο προκαλεί έντονο φθορισμό λόγω της υψηλής κβαντικής απόδοσης παρόλο που επιφέρει δραστική μείωση της ΔΦΑ σε σύγκριση με τους άλλους διαλύτες που μελετήθηκαν. Δύο από τις χρωστικές που μελετήθηκαν ως προς τη ΔΦΑ τους χρησιμοποιήθηκαν ως φωτοεκκινητής πολυμερισμού ενός ακρυλικού μονομερούς και την μελέτη του πολυμερισμού συναρτήσει διαφόρων παραμέτρων ακτινοβόλησης της ρητίνης. Οι χρωστικές αυτές έχουν φλουορένιο ως κεντρικό τμήμα και υποκαταστάτες στα άκρα φθαλιμίδιο ή τριφαινυλαμίνη. Και οι δύο χρωστικές δύναται να προκαλέσουν τον πολυμερισμό του μονομερούς με ακτινοβόληση υπερβραχέων παλμών στα 800nm, αλλά η προσθήκη αμίνης ως συνεκκινητή μειώνει το κατώφλι ισχύος εκκίνησης του. Επίσης, σε υψηλές τιμές ισχύος ακτινοβόλησης στο ίδιο μήκος κύματος παρατηρήθηκε αυτο-πολυμερισμός του μονομερούς γεγονός το οποίο έχει επισημανθεί μία μόνο ακόμη φορά σε μια εργασία με ρητίνη μίξης τριών ακρυλικών μονομερών. Δύο ρητίνες που παρασκευάστηκαν στην παρούσα διατριβή αναμιγνύοντας το μονομερές με τη κάθε χρωστική και με προσθήκη του συνεκκινητή μελετήθηκαν για την εξάρτηση του πολυμερισμού από τον φακό εστίασης και από την ισχύ, την ταχύτητα σάρωσης και τη διάμετρο της δέσμης. Για το σκοπό αυτό κατασκευάστηκαν δοκίμια στα οποία εγγράφονταν πολυμερισμένες γραμμές μεταβάλλοντας κάποια από τις παραπάνω παραμέτρους και μετρώντας το πάχος και το ύψος των γραμμών αυτών από τις εικόνες μικροσκοπίου σάρωσης ηλεκτρονίων. Το γεγονός ότι ο μικρότερης ισχύος φακός παρατηρηθηκε ότι προκαλεί λεπτότερη γραμμή εξηγείται από το φαινόμενο κατωφλίου του πολυμερισμού. Ωστόσο η λεπτότερη γραμμή επιτυγχάνεται με τον ισχυρότερο φακό καθώς μπορεί να μειωθεί περισσότερο η ισχύς της δέσμης λόγω του χαμηλότερου κατωφλίου εκκίνησης του πολυμερισμού για το φακό αυτό. Η αύξηση της ταχύτητας σάρωσης ή η μείωση της ισχύος της δέσμης επιφέρουν μικρότερες διαστάσεις πάχους και ύψους της γραμμής που πολυμερίζεται. Επίσης η κατανομή της ισχύος ακτινοβόλησης σε ολόκληρο το πίσω άνοιγμα του φακού επιφέρει καλύτερη εστίαση και λεπτότερη πολυμερισμένη γραμμή. Ωστόσο η κατάλληλη χωρική διαμόρφωση της δέσμης μπορεί να μειώσει τις διαστάσεις των πολυμερισμένων δομών. / -

Made available in DSpace on 2014-12-17T14:09:14Z (GMT). No. of bitstreams: 1 EdneyRVPG_TESE.pdf: 5370155 bytes, checksum: 315c7c0efbbd205da67094e4ae12330e (MD5) Previous issue date: 2012-09-03 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / A significant fraction of the hydrocarbon reserves in the world is formed by heavy oils. From the thermal methods used to recovery these resources, Steamflooding has been one of the main economically viable alternatives. In Brazil, this technology is widely used by Petrobras in Northeast fields. Latent heat carried by steam heats the oil in the reservoir, reducing its viscosity and facilitating the production. In the last years, an alternative more and more used by the oil industry to increase the efficiency of this mechanism has been the addition of solvents. When co-injected with steam, the vaporized solvent condenses in the cooler regions of the reservoir and mixes with the oil, creating a low viscosity zone between the steam and the heavy oil. The mobility of the displaced fluid is then improved, resulting in an increase of oil recovery. To better understand this improved oil recovery method and investigate its applicability in reservoirs with properties similar to those found in Potiguar Basin, a numerical study was done to analyze the influence of some operational parameters (steam injection rate, injected solvent volume and solvent type) on oil recovery. Simulations were performed in STARS ("Steam, Thermal, and Advanced Processes Reservoir Simulator"), a CMG ("Computer Modelling Group") program, version 2009.10. It was found that solvents addition to the injected steam not only anticipated the heated oil bank arrival to the producer well, but also increased the oil recovery. Lower cold water equivalent volumes were required to achieve the same oil recoveries from the models that injected only steam. Furthermore, much of the injected solvent was produced with the oil from the reservoir / Uma por??o significativa das reservas de hidrocarbonetos atualmente existentes no mundo ? formada por ?leos pesados. Dentre os m?todos t?rmicos utilizados para a recupera??o desse tipo de recurso, a Inje??o Cont?nua de Vapor tem se constitu?do como uma das principais alternativas economicamente vi?veis. No Brasil, essa tecnologia ? largamente utilizada pela Petrobras em campos localizados na regi?o Nordeste. O calor latente transportado pelo vapor aquece o ?leo do reservat?rio, reduzindo sua viscosidade e facilitando a produ??o. Nos ?ltimos anos, uma alternativa cada vez mais utilizada pela ind?stria para aumentar a efici?ncia desse mecanismo tem sido a adi??o de solventes. Quando coinjetado com o vapor, o solvente vaporizado se condensa nas regi?es menos aquecidas do reservat?rio e mistura-se ao ?leo, criando uma zona de baixa viscosidade entre o vapor e o ?leo pesado. A mobilidade do fluido deslocado ? ent?o melhorada, implicando num aumento da fra??o recuperada. Para melhor compreender esse mecanismo de recupera??o avan?ada e investigar a sua aplicabilidade em reservat?rios com caracter?sticas semelhantes aos encontrados na Bacia Potiguar, foi realizado um estudo num?rico, onde se verificou a influ?ncia de alguns par?metros operacionais (vaz?o de inje??o de vapor, volume de solvente injetado e tipo de solvente) sobre a recupera??o de ?leo. As simula??es foram realizadas no m?dulo STARS ( Steam, Thermal, and Advanced Processes Reservoir Simulator ) do programa da CMG ( Computer Modelling Group ), vers?o 2009.10. Verificou-se que a adi??o de solventes ao vapor injetado n?o s? antecipou a chegada do banco de ?leo aquecido ao po?o produtor como tamb?m incrementou a recupera??o de ?leo. Menores volumes de ?gua fria equivalente foram requeridos para se obter as mesmas fra??es recuperadas dos modelos que s? injetaram vapor. Al?m disso, boa parte do solvente injetado foi produzido juntamente com o ?leo do reservat?rio

Made available in DSpace on 2015-05-14T13:16:23Z (GMT). No. of bitstreams: 1 arquivototal.pdf: 3324327 bytes, checksum: b85304a7fe276b9b7697e2cdf5a23471 (MD5) Previous issue date: 2013-12-06 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / This study aimed at verifying exposure levels for gasoline and ethanol vapors and their psychophysical, neurocognitive, and physiological consequences in a sample of Brazilian pump attendants. Gas chromatography and microclimate sensing were used to passive and active monitoring of environmental levels of vapors. The psychophysical evaluation comprised the chromatic tests Lanthony D15-d and Cambridge Color Test 2.0, the Contrast Sensitivity Function using vertical sinusoidal gratings and Metropsis at the frequencies 0.2, 0.5, 1.0, 2.0, 5.0, 10.0, and 16.0 cpd, and eye-tracking at 250 Hz. Except by the D15-d test, all vision tests were performed with the dominant eye. The neurocognitive evaluation included the Trial Making Tests (A and B) and the Rey's Complex Figure Test. After applying exclusion criteria, the physiological evaluation was carried out in 16 attendants, who had a blood test to assess hepatic-biliary functions by the following markers: Alanine Aminotransferase (ALT), Aspartate Aminotransferase (AST), Direct Bilirubin (DB), Total Bilirubin (TB), and Gamma-glutamyl transpeptidase (GAMMA GT). The screening phase also included a questionnaire of Psychological and Neurophysiological Symptoms (PNS), a sociodemographic questionnaire, the Ishihara and the Rasquin 'E' tests. Thirty-eight pump attendants (Exposed Group) were selected, all males, with mean age of 32.66 years (SD = 1.30) and average schooling of 9.68 years (SD = 0.34). Thirty-eight volunteers (Control Group) were selected, all males, with mean age of 30.0 years (SD = 1.54), average schooling of 9.84 years (SD = 0.34), without reporting exposure to solvents and considered healthy following the inclusion criteria. The groups did not differ in age (p = .224) or schooling (p = .52), and all participants had normal or corrected-to-normal visual acuity 20/20. The Mann-Whitney test showed significant differences between scores in the Index of Color Confusion of the D15-d (p < .01, with losses in the tritan axis 75%), the Area of ellipses (protan, deutran, and tritan, all at p < .05), the frequencies 5, 10, and 16 cpd (p < .01), the Trail Making A (p < .01) and B (p < .05), the copy and memory of the Rey's complex figure (both at p < .01), and the number of saccades and trajectory time in the visual labyrinth (both at p < .01) as measure by the eye-tracker. The physiological evaluation showed changes in the values of DB (100 % of the pump attendants) and TB (62,5 %). Two attendants had combined changes in hepatic enzymes and biliburin. The Spearman correlation showed a significant association between the time of service and the areas protan (ρ = .46, p < .01) and deutan (ρ = .64, p < .01), the spatial frequency 5 cpd (ρ = .36, p < .05), and the Trail Making A (ρ = .40, p < .05) and B (ρ = .37, p < .05). The weight showed a tendency to attenuate the visual deficits, having a negative correlation with the area deutan (ρ = - .45, p < .01) and a positive one with contrast sensitivity at 0.20 cpd (ρ = .37, p < .05). Correlations were also found between DB and the time to perform the eye-tracker task (ρ = .58, p < .05) and the GGT and complaints of psychoneurovegetative instability (ρ = .57, p < .05). The Kruskal Wallis, and Mann-Whitney as a post-hoc test with Bonferroni's correction, showed that from 8 years of exposure there are consequences to color vision (Protan and Deutan) and for neurocognitive processes related to attention (Trail Making). The questionnaire PNS showed that 52.6% of pump attendants had symptoms of neuropsychological aggressions. Furthermore, there was a convergence between memory and attention complaints, with lower scores in the memory for the Rey's complex figure (ρ = - .34, p < .05). This study brings additional and new evidences for the consequences on color vision and contrast sensitivity, shows a potential occupational etiology in hepatic-biliary changes, presents neurocognitive xviii deficits in Brazilian pump attendants, and concludes that such deficits are correlated with chronic exposure (significant from 8 years of service) with a level of exposure to gasoline and ethanol below the Brazilian tolerance limit, but within an intervention level to gasoline vapor (168 and 153,40 ppm > 150 ppm) according to the Brazilian Standards for Work Health and Safety. / O objetivo deste estudo foi determinar os níveis de exposição aos vapores da gasolina e do etanol e verificar as consequências psicofísicas, neurocognitivas e fisiológicas em uma amostra de frentistas brasileiros. Para avaliar o nível de exposição ambiental foram realizados monitoramentos passivos e ativos de vapor com cromatografia gasosa e sensoriamento microclimático. A avaliação psicofísica foi realizada com os testes cromáticos de Lanthony D15-d e o Cambridge Color Teste 2,0; com a Função de Sensibilidade ao Contraste utilizando grades senoidais verticais e o Metropsis nas frequências 0,2; 0,5; 1,0; 2,0; 5,0; 10,0 e 16,0 cpg e com o rastreamento ocular utilizando um eyetracker 250 Hz. Todos os testes de visão, exceto o D15-d, foram realizados monocularmente com o olho dominante. A avaliação neurocognitiva ocorreu com os testes Trail Making A, B e com a Figura Complexa de Rey. A avaliação fisiológica, após utilização de parâmetros de exclusão, foi realizada pela análise de sangue de 16 frentistas verificando funções hepatotóxicas pelos marcadores Alanina Aminotransferase (ALT), Aspartato Aminotransferase (AST), Bilirrubina Direta (BD), Bilirrubina Total (BT) e Gamaglutamiltraspeptidase (GGT). Utilizou-se ainda o questionário de sintomas Psicológicos e Neurofisiológicos (PNF) além de um questionário sóciodemográfico e os testes de Ishihara e o ―E‖ de Rasquin na triagem. Essa etapa selecionou 38 frentistas do sexo masculino (Grupo Exposto), com idade média de 32,66 anos (DP = 1,30), grau de escolaridade média igual a 9,68 anos de estudo (DP = 0,34) e 38 voluntários (Grupo Controle) também do sexo masculino, sem histórico de exposição a solventes, considerados saudáveis pelos parâmetros de exclusão, com idade média de 31,00 anos (DP = 1,54) e grau de escolaridade médio de 9,84 anos de estudo (DP = 0,34). Não existiu diferença significativa entre a idade (p = 0,224) e o grau de escolaridade (p = 0,52) dos grupos que apresentaram ainda acuidade visual de 20/20 ou corrigida. Pelo teste de Mann-Whitney foram encontradas diferenças significativas entre os escores para: o Índice de Confusão de Cores do teste D15-d (p < 0,01, prevalecendo perdas no eixo tritan 75%), as Áreas das elipses (protan, deutan e tritan, ambos p < 0,05), as frequências 5 cpg, 10 cpg e 16 cpg (ambos p < 0,01), o teste Trail Making A (p < 0,01) e B (p < 0,05), a cópia e a memória da Figura complexa de Rey (ambas p < 0,01) e o número de sacadas e tempo de percurso do labirinto no eyetracker (ambos p < 0,01). A avaliação biológica demonstrou principalmente alterações nos valores da BD (100 % dos frentistas) e BT (62,5 %). Dois frentistas tiveram alterações combinadas de enzimas hepáticas e bilirrubinas. A correlação de Spearman demonstrou a influência do tempo de serviço no acréscimo das áreas protan (ρ = 0,46; p < 0,01) e deutan (ρ = 0,64; p < 0,01), além de correlações com a frequência de 5 cpg (ρ = 0,36; p < 0,05) e com os testes Trail Making A (ρ = 0,40; p < 0,05) e B (ρ = 0,37; p < 0,05). O peso apresentou a tendência de atenuar os déficits nos testes de visão, correlacionando negativamente com a área deutan (ρ = - 0,45; p < 0,01) e positivamente com a sensibilidade ao contraste na frequência 0,20 cpg (ρ = 0,37; p < 0,05). Existiram ainda correlações entre a BD e o tempo para realizar a prova no eyetracker (ρ = 0,58; p < 0,05) e entre o GGT e as queixas de instabilidade psiconeurovegetativa (ρ = 0,57; p < 0,05). Os testes Kruskal Wallis, e Mann- Whitney como post hoc com correção Bonferroni, demonstraram que a partir de 8 anos de exposição existem consequências para a visão de cores (Protan e Deutan) e para processos neurocognitivos relacionados a atenção (Trail Making A). O questionário PNF apontou que 52,60 % dos frentistas possuem sintomas de agressões neuropsicológicas. Além disso, existiram convergências entre as queixas de falta de memória e concentração, com menores pontuações da memória na Figura Complexa de Rey (ρ = - 0,34; p < 0,05). Este estudo confirma e avança nas descobertas de consequências na visão de cores e sensibilidade ao contraste, aponta uma possível etiologia ocupacional nas alterações hepatotóxicas, apresenta as deficiências neurocognitivas nos frentistas brasileiros e conclui que essas deficiências e as da visão de cores estão correlacionadas a uma exposição crônica (significativa aos 8 anos de serviço) com um nível de exposição a gasolina e ao álcool etílico abaixo do Limite de Tolerância brasileiro, mas a um nível de intervenção para o vapor de gasolina (168,00 e 153,40 ppm > 150 ppm) conforme as Normas de Saúde e Segurança do Trabalho brasileiras.

Chlorinated aliphatic hydrocarbons (CAH´s) were used widely within dry cleaning facilities and for metal degreasing until their toxicity was discovered. PCE is still used as dry cleaning liquid. Today CAH´s are found in soil environment at places where they have been used in the past. The CAH-concentration in trees growing on contaminated land has quite recently received attention as a cheap and effective way of assessing the extent of a CAH-contamination. The method has however, not been put into use in Sweden. The aim of the study has been to investigate whether the CAH-concentration in tree cores could be used to delineate the spread of CAH in a soil environment under Swedish conditions in different seasons. The aim has also been to gain an understanding of the uptake process, as well as to identify the limitations of the method and important issues to consider when sampling. Trees were sampled in March and June on Helgö 1:25, 1:26 in Växjö, Småland. Metal degreasing earlier conducted at this site has lead to the CAH contamination of soil and groundwater (PCE, TEC c-DACE). Mostly PCE, TCE, and chloroform were detected in tree cores. The CAH concentration was higher in June. Using the sum of PCE+TCE+c-DCE in trees to delineate the spread gave a result that was quite consistent with a delination done based on groundwater sampling. The uptake of CAH by trees is governed by the uptake of water at the root. The water usage, together with the origin of the water used is important for the ability of the tree to take up CAH. The CAH concentration within trees is also dependent on the chemical properties of the compound (Log kow, solubility etc), the concentration of the compound in the soil as well as degradation processeses. The position and height of sampling in the trees, tree species as well as tree size are important factors to consider when sampling. Sampling during summer is preferred when the concentration of CAH in trees is likely to be higher. The analysis of CAH in tree cores has potential to be used as a screening tool in soil investigations under Swedish conditions. It is a cheap and easy to use method, which would be a good complement to other investigative measures. However, an increased understanding of the processes involved, together with more analysis are needed., as this is a new method. / Klorerade lösningsmedel (CAH) användes i stor omfattning som bl a kemtvättmedel och avfettningsmedel tills dess att deras toxiska egenskaper blev kända. Perkloretylen (PCE) används än idag som kemtvättmedel. CAH återfinns ofta i markmiljö på de platser där de tidigare använts. Analys av CAH-koncentration i trädkärnor har uppmärksammats som en billig och effektiv metod för att översiktligt bedöma utbredningen av dessa föroreningar. Metoden har inte tidigare använts i Sverige. Syftet med detta examensarbete är att undersöka om trädprovtagning kan användas för att bedöma utbredningen av föroreningar i markmiljö under svenska förhållanden vid olika årstider. Analyserade CAH-halter i träd har jämförts med tidigare registrerade halter av CAH i grundvatten. Syftet har också varit att beskriva CAH-upptaget i träd, undersöka metodens begränsningar samt att sammanfatta viktiga aspekter vid provtagning. Provtagningar av träd har genomförts under mars och juni på fastigheterna Helgö 1:25 och 1:26 i Växjö, där tidigare metallavfettning har medfört att mark och grundvattnet förorenats av CAH; perkloretylen (PCE), trikloretylen (TCE) och nedbrytningsprodukten dikloretylen (c1,2-DCE). Vid analys av trädkärnor detekterades främst PCE, TCE samt TCM (kloroform). Koncentrationen av CAH var högre i juni. Halten PCE+TCE+c-DCE i trädproverna gav en översiktlig bild av föroreningssituationen som överensstämde väl med de grundvattenprover som tidigare tagits på fastigheten. CAH tas upp i vattenlöst fas vid trädens rötter. Trädets vattenbehov och vilket vatten det utnyttjar är därför viktigt för dess möjlighet att ta upp CAH. Ämnets kemiska egenskaper (log kow, flyktighet, mm.), samt förekomst och nedbrytning påverkar den halt som registreras i trädet. Vid provtagning bör provtagningspunkternas höjd över marken och position, trädart samt trädstorlek beaktas. Provtagning under sommaren är att föredra eftersom halterna då är högre. Jämförelsen med grundvattenprovtagning visar att metoden har potential att användas i Sverige för att bedöma utbredningen av en CAH-förorening i markmiljö. Den är enkel att använda och kan vara ett alternativ på platser där konventionella metoder är svåra att genomföra. En ökad förståelse för involverade processer, samt utökade undersökningar av metoden är nödvändiga då metoden är ny.

CoordenaÃÃo de AperfeÃoamento de Pessoal de NÃvel Superior / Aromatic hydrocarbons are chemical compounds of great interest in the petrochemical industry. These are commonly derived from reformed naphtha, which are in multicomponent mixtures with aliphatic hydrocarbons. The separation of these components is realized, generally, the liquid-liquid extraction process. In this process, the sulfolane is the most widely used solvent. However, this has some disadvantages such as high cost. For this reason, many studies are developed by the academic community in order to propose alternative solvents to replace the exclusive use of sulfolane by compounds that are important features like good selectivity, easy recoverability and low costs. Given the above, this study main aims to determine liquid-liquid equilibrium data (LLE) to study the ability of solvents [diethylene glycol (DEG), triethylene glycol (TEG), glycerol and 2-hydroxyethyl amine format (2-HEAF)] in extracting aromatic mixtures with aliphatic. The physical properties also of great importance in the understanding of the behavior and interactions that occur in liquid mixtures. Thus, in this study were also studied the density and viscosity of solvent extractors aromatic. The experimental methodology for the determination of LLE data was initially validated by reproducing the literature, and the results showed good agreement between these data. After the method has been validated, solubility curves and tie-lines were constructed for systems containing decane + toluene + DEG (+ TEG, + glycerol, + 2-HEAF, + sulfolane) at T = (303.15 and 333.15) K. The composition data of tie-lines, obtained experimentally, were used to calculate the selectivity parameter and the distribution coefficient. With this data, it can be concluded that all the solvents studied have a good capacity for toluene extraction from mixtures with decane. However, the glycerol has presented as the most promising solvent for aromatics extraction. Finally, the experimental data were correlated through the thermodynamic activity coefficient models, NRTL and UNIQUAC. The results were considered satisfactory, noting that the NRTL was the model that presented minor deviations in compositions. Thus, best represented the LLE data for the systems studied. / Os hidrocarbonetos aromÃticos sÃo compostos quÃmicos de grande interesse na indÃstria petroquÃmica. Estes sÃo comumente originados da nafta reformada, onde encontram-se em misturas multicomponentes com hidrocarbonetos alifÃticos. A separaÃÃo destes componentes à realizada, em sua grande maioria, pelo processo de extraÃÃo lÃquido-lÃquido. Nesse processo, o sulfolano à o solvente mais utilizado. No entanto, este apresenta algumas desvantagens, tais como alto custo. Por esse motivo, inÃmeros estudos sÃo realizados pela comunidade acadÃmica a fim de propor solventes alternativos que substituam o uso exclusivo do sulfolano por compostos que tambÃm apresentem caracterÃsticas importantes, como boa seletividade, boa recuperabilidade e baixos custos. Diante do exposto, o presente trabalho tem como principal objetivo determinar dados de equilÃbrio lÃquido-lÃquido (ELL) para estudar a capacidade dos solventes [dietilenoglicol (DEG), trietilenoglicol (TEG), glicerina e 2-hidroxietilamina formato (2-HEAF)] em extrair aromÃticos das misturas com alifÃticos. As propriedades fÃsicas tambÃm assumem extrema importÃncia no conhecimento do comportamento e das interaÃÃes que ocorrem nas misturas de lÃquidos. Deste modo, neste trabalho foram estudados a densidade e a viscosidade de solventes extratores de aromÃticos. A metodologia experimental para obtenÃÃo dos dados de ELL foi inicialmente validada reproduzindo dados da literatura, e os resultados mostraram uma boa concordÃncia entre estes dados. ApÃs a metodologia ter sido validada foram construÃdas curvas de solubilidade e tie-lines para os sistemas contendo decano + tolueno + DEG (+ TEG, + glicerina, + 2-HEAF, + sulfolano) a T = (303,15 e 333,15) K. Os dados de composiÃÃo das tie-lines, obtidos experimentalmente, foram utilizados para calcular o parÃmetro de seletividade e o coeficiente de distribuiÃÃo. De posse desses dados, pode-se concluir que todos os solventes estudados apresentam boa capacidade para extraÃÃo de tolueno a partir de misturas com decano. No entanto, a glicerina destacou-se como o solvente mais promissor para a extraÃÃo de aromÃticos apresentando os maiores valores para seletividade. Finalmente, os dados experimentais foram correlacionados atravÃs dos modelos termodinÃmicos de coeficiente de atividade, NRTL e UNIQUAC. Os resultados foram considerados satisfatÃrios, observando-se que o NRTL foi o modelo que apresentou os menores desvios na composiÃÃo. Dessa forma, representou melhor os dados de ELL para os sistemas estudados.

Submitted by Renata Lopes (renatasil82@gmail.com) on 2016-05-20T13:32:38Z No. of bitstreams: 1 janedaisydesousaalmadaresende.pdf: 213211 bytes, checksum: 7f0d7ee1b43dfa3fc109755fd5562c3c (MD5) / Approved for entry into archive by Adriana Oliveira (adriana.oliveira@ufjf.edu.br) on 2016-07-02T11:22:02Z (GMT) No. of bitstreams: 1 janedaisydesousaalmadaresende.pdf: 213211 bytes, checksum: 7f0d7ee1b43dfa3fc109755fd5562c3c (MD5) / Made available in DSpace on 2016-07-02T11:22:02Z (GMT). No. of bitstreams: 1 janedaisydesousaalmadaresende.pdf: 213211 bytes, checksum: 7f0d7ee1b43dfa3fc109755fd5562c3c (MD5) Previous issue date: 2012-01-26 / O presente trabalho teve o objetivo de verificar a sensibilidade de larvas de Amblyomma cajennense e Dermacentor nitens frente os solventes etanol, metanol, acetona, xilol e dimetilsulfóxido (DMSO) e o agente tensoativo Tween 80. Os solventes etanol, metanol, acetona e xilol foram testados em pureza analítica, enquanto o DMSO e o agente tensoativo Tween 80 foram testados na concentração de 1%, sendo estabelecido que as substâncias testadas em pureza analítica que causassem alta mortalidade seriam testadas também nas concentrações de 50, 25 e 1%. Foi utilizado o teste de pacote de larvas, sendo feitas dez repetições para cada tratamento. Também foi formado um grupo controle com o mesmo número de repetições, em que as larvas foram tratadas com água destilada. No primeiro experimento, nas concentrações testadas, apenas o xilol se mostrou como substância de alta toxicidade, uma vez que a mortalidade observada foi superior a 90% para larvas de A. cajennense e D. nitens. No segundo experimento, o xilol a 1 e a 25% apresentou baixa toxicidade para larvas de A. cajennense e D. nitens, respectivamente, uma vez que o percentual de mortalidade foi estatisticamente semelhante (p>0,05) ao do controle. / The objective of this work was to verify the sensitivity of Amblyomma cajennense and Dermacentor nitens larvae to the solvents ethanol, methanol, acetone, xylol and dimethyl sulfoxide (DMSO) and the surfactant Tween 80. The first four solvents were tested at analytical purity while the DMSO and surfactant Tween 80 were tested at a concentration of 1%. The substances tested at analytical purity that caused high mortality were also tested at concentrations of 50, 25 and 1%. The larval packet test was used, with ten repetitions for each treatment. A control group was also formed with the same number of repetitions, in which the larvae were only exposed to distilled water. In the first experiment, only xylol was highly toxic at the concentrations tested, causing mortality above 90% for larvae of both species. In the second experiment, xylol at 1 and 25% showed low toxicity to the A. cajennense and D. nitens larvae, respectively, since the mortality percentage was statistically similar to that of the control group (p>0.05).

Submitted by Renata Lopes (renatasil82@gmail.com) on 2017-04-17T11:56:32Z No. of bitstreams: 1 biancacarvalhodasilva.pdf: 1674027 bytes, checksum: c5eec1256778b071c02c01d37079c6bc (MD5) / Approved for entry into archive by Adriana Oliveira (adriana.oliveira@ufjf.edu.br) on 2017-04-18T13:39:20Z (GMT) No. of bitstreams: 1 biancacarvalhodasilva.pdf: 1674027 bytes, checksum: c5eec1256778b071c02c01d37079c6bc (MD5) / Made available in DSpace on 2017-04-18T13:39:20Z (GMT). No. of bitstreams: 1 biancacarvalhodasilva.pdf: 1674027 bytes, checksum: c5eec1256778b071c02c01d37079c6bc (MD5) Previous issue date: 2016-02-24 / Musca domestica é um importante vetor mecânico de diversos patógenos para humanos e animais de criação, sendo essencial o estudo de novas alternativas de controle mais eficientes e seguras para este díptero. A busca por novas alternativas de inseticidas envolve experimentos que geralmente necessitam do uso de solventes que não interfiram nos resultados da substância testada. Assim, o presente estudo compreendeu duas etapas: investigar a sensibilidade de larvas e pupas de M. domestica aos solventes acetona, etanol, metanol e dimetilsulfóxido (DMSO) e ao surfactante Tween 80 em diferentes tempos de volatilização; e avaliar a toxicidade dos fenilpropanoides eugenol e (E)-cinamaldeído sobre os mesmo estágios deste díptero. Para ambos os experimentos utilizou-se o teste de contato, com 10 repetições (n=10) para cada solvente/surfactante e concentração das substâncias sobre cada estágio. No primeiro experimento foram testados acetona, etanol e metanol em pureza analítica e DMSO e Tween 80 na concentração de 5%. Os tempos avaliados foram zero, cinco, 10 e 15 minutos (23±2°C e 60±10% UR). Os resultados mostraram que o tempo de volatilização produz diferença significativa na mortalidade larval (ML) para os três primeiros solventes testados, e acetona mostrou-se semelhante ao controle após cinco minutos de volatilização (p>0,05). Metanol e etanol mostraram-se semelhantes ao controle após 15 minutos de volatilização (p>0,05). DMSO não apresentou ML significativa (p>0,05), no entanto apresentou percenbtual de mortalidade acumulada (PMA) superiores a 14% (p<0,05). Tween 80 não apresentou diferença na toxicidade sobre as larvas relacionada ao tempo. Para o teste com pupas somente etanol produziu diferença significativa entre os tempos de volatilização, enquanto acetona e metanol diferiram do controle em todos os tratamentos (p<0,05). DMSO e Tween 80 não diferiram significativamente do controle em nenhum tempo (p˃0,05). O surfactante Tween 80 foi o único que não apresentou toxicidade para ambos os estágios na concentração testada, porém acetona foi o solvente que volatilizou mais rapidamente, mostrando menor toxicidade entre aqueles testados em pureza analítica. Para o segundo experimento, foram utilizadas oito concentrações de cada substância para a determinação das concentrações letais (CL50 e CL90). Eugenol apresentou os menores valores de CL50 e CL90, para a eficácia do tratamento larval (ETL) (1,5 e 3,75 mg/mL, respectivamente) enquanto (E)-cinamaldeido apresentou os menores valores de CL50 e CL90 para a eficácia do tratamento pupal (ETP) (18,08 e 78,83 mg/mL, respectivamente). Ambas as substâncias apresentaram atividade larvicida a partir de 2,5 mg/mL e ETL de 100% a partir de 5 mg/mL. Para o tratamento pupal (E)-cinamaldeído diferiu do controle a partir da 13 concentração de 10mg/mL (p<0,05) e ambos os fenilpropanoides causaram má formação em adultos a partir de 10 mg/mL, e maior ETP na concentração de 30 mg/mL, sendo 67,2% para (E)-cinamaldeído e 32% para eugenol. Os produtos testados nesse estudo apresentaram elevado potencial larvicida, além de ambos apresentarem efeitos pupicida e causarem má formação nos adultros provenientes de pupas tratadas. Ainda, é possível sugerir a utilização conjunta de ambas substância para um controle mais eficiente, visto que (E)-cinamaldeído apresentou melhor atividade larvicida, enquanto eugenol teve melhor atividade pupicida. Desta forma, esses fenilpropanoides mostrando-se promissores para o uso no desenvolvimento de formulações mais seguras para a saúde e meio ambiente, sendo possível sua utilização em estratégias de Manejo Integrado de Pragas. / Musca domestica is an important mechanical vector of several pathogens to humans and domestic animals, being essential to study new alternatives to eficiente and safe control against this Diptera. The search for new insecticides alternative involves experiments that generally require the use of solvents that should not interfere in the results of the test substance. Thus, this study involved two stages: to investigate the sensitivity of M. domestica larvae and pupae to the solvents acetone, ethanol, methanol and dimethylsulfoxide (DMSO) and the surfactant Tween 80 at different times of volatilization; and evaluating toxicity of phenylpropanoid eugenol and (E)-cinnamaldehyde against the same stages of this Diptera. For both experiments were used the patch test with 10 repetitions (n=10) for each solvent/surfactant and concentration of substances against each stage. In the first experiment acetone, ethanol and methanol were tested in analytical purity while DMSO and Tween 80 at the concentration of 5%. The times evaluated were zero, five, 10 and 15 minutes (23±2°C and 60±10% RH). The results showed that the volatilization time produces significant difference in larval mortality (LM) for the first three solvents tested, and acetone was similar to the control after five minutes volatilization (p>0.05). Methanol and ethanol were similar to the control after 15 minutes of evaporation (p>0.05). DMSO showed no significant LM (p> 0.05), but its accumulated mortality percenbtual (AMP) was over 14% (p<0.05). Tween 80 showed no difference in toxicity againts larvae related to time. For the pupae test only ethanol produced significant difference between the evaporation time, while acetone and methanol differed from the control in all treatments (p<0.05). DMSO and Tween 80 did not differ significantly from control at any time (p>0.05). The surfactant Tween 80 was the only one that showed no toxicity for both stages at the concentration tested, however the solvent acetone was volatilized more quickly, showing lower toxicity among those tested in analytical purity. For the second experiment, we used eight concentrations of each substance for the determination of lethal doses (LC50 and LC90). Eugenol showed the lowest values of LC50 and LC90 for the effectiveness of larval treatment (ELT) (1.5 and 3.75 mg/mL, respectively) while (E)-cinnamaldehyde had the lowest values of LC50 and LC90 for effectiveness of pupal treatment (EPT) (18.08 and 78.83 mg/mL, respectively). Both substances exhibited larvicidal activity from 2.5 mg/mL and ELT of 100% from 5 mg/mL. For pupal treatment (E)cinnamaldehyde differed from the control from the concentration of 10mg/mL (p <0.05) and both phenylpropanoid caused malformation in adults from 10 mg/mL. The greater EPT was from concentration of 30 mg/mL, being 67.2% for (E)-cinnamaldehyde and 32% for eugenol. 15 The products tested in this study had high potential larvicide, and both present pupicida effects and cause malformation in adultros from treated pupae. Still, it is possible to suggest the combined use of both substance for more efficient control, as (E)-cinamaldeído showed better larvicidal activity, while eugenol had better pupicida activity. Thus, using these phenylpropanoids show promise in the development of safer formulations for health and the environment, and these could be used in Integrated Pest Management strategies.

La bio-transformation naturelle des médicaments peut produire des métabolites toxiques; l’identification de ces métabolites est essentielle dans la stratégie de choix de molécules thérapeutiques. En appliquant les technologies de fermentation en bioréacteur des cellules hétérologues (souches d’E. coli recombinantes exprimant une iso-enzyme de cytochrome P450 humain avec la réductase humain), la bioconversion du substrat (principe actif) en ses métabolites de dégradation, a été réalisée à grande échelle (& / Doctorat en Sciences / info:eu-repo/semantics/nonPublished