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In this work, an investigation on the fraction of tyre pyrolysis oil with a similar distillation range to that of automotive diesel (150 – 360 oC) was carried out to determine its suitability as an alternative or additive to petro-diesel fuel. The quality of this oil was evaluated by comparing its key properties to the requirements of South African National Standards for Automotive diesel fuel (SANS-342) and to conventional automotive diesel fuel. The viscosity, density, copper strip corrosion of this fuel were found to be within the acceptable limits set by SANS while sulphur content and flash point were out of their respective set limits. In addition, mixing rule equations for predicting viscosity and density for both pure and blends of the oil as a function of temperature were developed and evaluated. The equations were found to be suitable due to their low Absolute Percentage Deviation. Engine performance tests were carried out with blends of Distilled Tyre Pyrolysis Oil (DTPO) and petro-diesel fuel in a single cylinder air cooled diesel engine. The performance, emission and combustion characteristics of the diesel engine while running on these blends were evaluated and subsequently, a comparative analysis was performed with conventional petro-diesel fuel as the reference fuel. It was found that, the engine could run with up to 60% (DTPO) without any problem. Beyond this level the engine became unstable. The power and torque were similar at low and medium speeds. However, at high speeds, the power dropped with increase in DTPO in the blend. Fuel consumption was very comparable for all the test fuels. Carbon monoxide and unburned hydrocarbons were higher for the blends compared to petro-diesel fuel but oxides of Nitrogen were lower. The peak pressure for petro-diesel fuel was marginally higher than that of the blends. Present results indicate that, petro-diesel fuel can be blended with up to 60% DTPO and produce acceptable performance. Testing the diesel engine under different operating conditions is a time consuming and expensive process that also requires the use of specialised equipment which may not be readily available. An Artificial Neural Network (ANN) model based on a back-propagation learning algorithm was developed to predict engine performance and emissions separately, based on fuel blend and speed. The performance and accuracy of the model were evaluated by comparing experimental and ANN predicted results. The ANN was able to predict both engine performance and emissions with acceptable levels of accuracy. The values of correlation coefficient between experimental and predicted data being greater than 0.99. From this work, it can be implied that engine emission and performance can be predicted using neural network-based mode, consequently, it will be able to do further investigations without running laboratory experiments. Energy recovery from waste is an interesting field for engineers and scientists. It is hoped that this work will prompt new research ideals on how tyre pyrolysis oil can be improved for use as diesel engine fuel and building better models for diesel engine performance and emissions

The gas chromatograms of crude oil hydrocarbons reveal both resolved and unresolved components. The unresolved feature is commonly referred to as the unresolved complex mixture (UCM). UCMs are thought to result from the co-elution of complex mixtures of hydrocarbons with similar chemical properties and become more obvious as resolved components are removed by processes such as weathering and refining. Consequently UCMs are a prominent feature in oil-polluted sediments, biodegraded crudes and refineiT products. The characterisation of both aliphatic and aromatic unresolved complex mixtures (UCMs) of hydrocarbons, as well as their possible effects on the environment, is described. An aliphatic hydrocarbon UCM isolated from the base oil of Silkolene 150 lubricating oil was characterised by a combination of micro vacuum-distillation and oxidative degradation. Vacuum-distillation produced six distillate cuts and a residue which were all highly unresolved by GC (ca. 951/6). The average molecular weight of each cut was determined by probe CIMS (310 - 440 Daltons), and varied by -20 Daltons. Cr03 oxidation of each fraction yielded similar distributions of n-monocarboxylic acids, ketones and lactones as well as C02 (ca. 6%). The resolved products of oxidation suggest that the aliphatic UCM is a rather homogeneous mixture of highly branched alkanes. However a significant amount of the products remain unresolved (UCMox.; ca. 70-95%). A retro -structural analysis approach, using an aromatic UCM oxidant (Ru04), combined with a mass balance approach, was used to characterise aromatic UCMs. Following reproducibility studies and the analysis of authentic aromatic compounds, the method was applied to the characterisation of unresolved aromatic refinery oil fractions and a suite of aromatic UCM distillate fractions. Selected refinery oils were separated into mono-, di-, tri- and tetraaromatics by BPLC and shown to be mainly unresolved by GC (ca. 80%). Ru04 oxidation of these fractions yielded DCM soluble products (24 - 74%), water soluble products (0 - 10%) and C02 (12 -78%). The principal resolved products in each oxidation were monocarboxylic acids and dicarboxylic acids which were used to reconstruct precursor compounds. Vacuum-distillation of Tia Juana Pesado crude (Venezuela) gave six cuts and a residue which were analysed by GC, 1H NMP, UV and probe CIMS to obtain molecular weight (171 - 301 Daltons) and broad structural information whilst Ru04 oxidation was used to obtain molecular information via the retro -structural analysis approach. This showed that the aromatic UCM was in fact highly aliphatic and contained alkyl and cycloalkyl tetralins. A significant advancement in the quantitative characterisation of UCMOx. and subsequently the characterisation of aromatic UCMs was made. Ion cyclotron resonance spectrometry (ICR) was used to characterise the Ru04 oxidation products of selected refinery fractions. Analysis of the oxidation products of a monoaromatic refinery fraction indicated the presence of monocarboxylic acids (Cl - C21; 58%) and alicyclic carboxylic acids (C7 - C19; 16%), a hydrogenated monoaromatic sample contained monocarboxylic acids (Cl - C20; 30%), dicarboxylic acids (C2 - C11,7%) and alicyclic carboxylic acids (C7 - C18; 11%) , whilst a diaromatic fraction contained monocarboxylic acids (C10 - C19; 7%), alkyl phthalic acids (C8 - C17', 17%) and cycloalkyl phthalic acids (C11 - C15; 3%). Retro -structural analysis suggests that the nonhydrotreated monoaromatic UCM is mainly comprised of alicyclic and alkyl substituted benzenes, the monoaromatic UCM isolated from the hydrotreated oil of alky'l and cycloalkyl substituted tetralins and the diaromatic fraction of alkyl and cycloalkyl naphthalenes. This was supported by, FIMS analysis of the fractions prior to oxidation. As an investigation of the environmental toxicity of UCMs, the effect of a saturated aliphatic UCM, and its chemical oxidation products, on the feeding rate of mussels (Mytilus edulis), was investigated. The UCM had little effect, whilst oxidation resulted in an increase in toxicity. The non-toxic nature of the hydrocarbons was attributed to their low aqueous solubility, whilst oxidation resulted in the formation of products NNith a greater solubility, which were sufficiently hydrophobic to be narcotic toxicants. Parts of this work have been published [Thomas et al., (1993) Organic Geochemistry, Falch Hurtigtrykk, Non%-ay(A bstract), 717-719; Thomas et al., (1995) [Vater Research. 29,371-382]. iv

Η θάλασσα αποτελεί ένα από τα βασικότερα στοιχεία της παγκόσμιας οικονομικής ανάπτυξης, αλλά και ένα από τα σημαντικότερα περιβαλλοντικά αγαθά. Η ρύπανση των θαλασσών με την συνεπακόλουθη υποβάθμιση των παράκτιων περιοχών αποτελούν δύο από τα σημαντικότερα περιβαλλοντικά προβλήματα που αντιμετωπίζει ο πλανήτης μας. Οι πετρελαϊκοί υδρογονάνθρακες αποτελούν μια κατηγορία ρύπων με ιδιαίτερη σημασία παγκοσμίως εξαιτίας της τοξικότητας τους και των επιπτώσεων τους στο οικοσύστημα. Στην παρούσα διπλωματική διατριβή γίνεται μια προσπάθεια διερεύνησης της διασποράς πετρελαιοειδών ρύπων στον Κορινθιακό Κόλπο, ο οποίος αποτελεί αφενός ένα ιδιαίτερα κλειστό κόλπο με περιορισμένη επικοινωνία με την ανοιχτή θάλασσα και αφετέρου εάν ιδιαίτερα σημαντικό κόλπο της Ελλάδας, τόσο από πλευράς βιοποικιλότητας όσο και από άποψη αλιευτικής παραγωγής. Για τον λόγο αυτό πραγματοποιήθηκαν δειγματοληψίες κατά μήκος του Νότιου κυρίως τμήματος του Κόλπου, με σκοπό την διερεύνηση της διασποράς πετρελαιοειδών κατά μήκος των ακτών με τη χρήση ευέλικτων δεικτών. / Sea is one of the key elements of global economic growth and also one of the most important environmental assets. Marine pollution and the consequent degradation of coastal areas are two major environmental problems our planet is facing. Oil hydrocarbons are some of the most important pollutants worldwide, due to their toxicity, as well as their major environmental consequences. The objective of this study was to determine the dispersion of petroleum contaminants in the Gulf of Corinth. The Gulf of Corinth is an enclosed sea between the Ionian Sea and the Corinth Canal and is also considered to be a very important wildlife habitat. Sampling took place along the main southern part of the Gulf, to investigate the spread of oil hydrocarbons along the coast area with the use of flexible indicators.

Ce travail a permis d’étudier la dynamique saisonnière des communautés microbiennes (cytométrie en flux et MiSeq ADNr16S) d'un étang sursalé thalassohalin. Malgré les variations de salinité (15,5 à 32 %), un core microbiome hautement stable (97,2± 2,1%) et dominé par Haloquadratum (40,3 à 57,4%) et Salinibacter (4,9 à 21,8%) a été décrit. De plus, des populations halotolérantes, capables de croitre rapidement, ont été détectées durant les épisodes de dilution des eaux. Dans un contexte physico-chimique contraignant où la biodégradation des hydrocarbures (HC) reste controversée, une première étude a été réalisée afin de comprendre le devenir d’un pétrole et son effet sur les communautés microbiennes actives de saumures proches de la saturation en sels (31%). Après biostimulation de ces communautés par l’ajout de matière organique labile et d'une température favorable (40°C), des phytolyptes actifs appartenant aux genres Haloarcula, Halobacterium et Halorubrum ont été détectés dans les microcosmes présentant de la biodégradation (12,8%) après 30 jours. Face aux limitations des processus d'autoépuration en contexte naturel (température plus faible), plusieurs approches de biostimulation testées (i.e. fertilisation minérale –NS ou organique –DS ; dilution) ont permis de forts taux d'atténuation des HC aliphatiques (97,8% et 54,5%) dans des saumures diluées (27,7 à 14%) et fertilisées (-DS et -NS). Dans ces mêmes microcosmes, des phylotypes actifs majoritaires appartenant aux genres Marinobacter et à la famille des Flavobacteriaceae (dont Psychroflexus) ont été détectés (MiSeq ADNr16S). L'opérabilité de ces traitements mériterait d'être testée à une plus large échelle. / This work performed on a thalassohaline hypersaline lake firstly considered seasonal dynamics of microbial communities (flow cytometry and MiSeq on 16S rRNA). Despite salinity fluctuations (15.5-32 %), a microbiome core highly stable at the genus level (97.2 ± 2.1 %) and dominated by Haloquadratum (40.3-57.4 %) and Salinibacter (4.9-21.8 %) was described. Interestingly, some halotolerant phylotypes exhibited rapid growths during dilutions episodes. In a controversial context concerning high salinity effects on hydrocarbons (HC) biodegradation, a study was conducted on close to salts-saturation brines (31 %) to gain insight into the fate of oil and it effects on active microbial communities after 15- and 30-days incubations. Significant oil biodegradation (12.8 %) was detected only after a 30-days incubation in LOM-amended microcosms while phylotypes belonging to Halobacteriaceae (Haloarcula, Halobacterium and Halorubrum) appeared as major active phylotypes. However, these low rates suggested that oil biodegradation should be lower under in situ conditions (lower temperature). Thus, among biostimulation approaches (mineral (-NS) or organic (-DS) amendments; dilution) used to improve self-cleaning processus, DS- or NS-amendments added to diluted brines (27.7 % to 14.0 %) allowed high attenuation rates of aliphatic HC with 97.8 % and 54.5 % respectively. Bacterial phylotypes belonging to Marinobacter and Flavobacteriaceae (e.g. Psychroflexus) were detected in NS- and DS-amended microcosms in which petroleum biodegradation occurred. This strategy will have, however, to be tested in other hypersaline systems (natural or industrial) in order to test its operational efficiency.