Thesis (D.P.H.)--University of Michigan, 1994.

Thesis (D.P.H.)--University of Michigan, 1994.

Thesis (M. Phil.)--University of Hong Kong, 1997. / Includes bibliographical references (leaf 192-208).

For many years, the construction industry in Sweden has not developed much of an integral approach for design across disciplines. The sector’s impact on society, economics and environment is huge. To make the interactions within the construction industry more efficient, a relatively new concept called BIM (Building Information Modeling) has been introduced. The idea with BIM is that the different actors of the construction industry will work through intelligent CAD software, with common file formats and more cooperation between different actors during the various steps of the building and construction process. The technical consultancy company WSP Sweden is working actively to implement BIM within the frame of its activities. One step towards BIM is the use of their visualization software Novapoint Virtual Map in a better way. They lack a good system to show which pipes belongs to different documents, i.e. some kind of status management. Another step towards BIM is to be able to change and revise Water and Sewage 3D-models with HVAC 3D-models, and to be able to detect possible errors in the connection nodes early in the designing stage. In this thesis work, a CAD-model has been created in Novapoint VA, the CAD software used to design pipe and sewage systems at WSP. The designed model is divided into many stages which creates many parallel documents at the same time. The model is visualized in Novapoint Virtual Map where functions for status management are created. With the help of grouping functions in the software it is possible to show pipes that belong to different documents at the same time. The more documents there are in the same model the longer it takes to create the model, which is something that could be improved in later editions of the software. In this paper, seven tests were carried on to examine how water and sewage pipes CAD-models created in Novapoint VA can be jointly revised with HVAC CAD-models created in MagiCAD. The result of the test shows that four of these tests can be used to revise the models. To use one of these methods, according to the BIM model, for changes and revisions of models can help avoid mistakes in connection points already at design stage.

The hydrocarbons of recent polluted sediments, in-reservoir and laboratory biodegraded crude oils, and certain petroleum products (e.g. lubricating oils) often display 'humps' or Unresolved Complex Mixtures (UCMs) when analysed by gas chromatography (GC). Although widespread and often abundant, to date little is known of their detailed molecular composition. Standard chromatographic methods of isolation of model aliphatic and aromatic hydrocarbon UCMs from lubricating oils followed by conventional methods of analysis provided little compositional detail. Thus GC and GC-electron impact mass spectrometry (GC-EIMS) was limited to an estimate of carbon number ranges and to the identification of certain series of 'biological marker' compounds. However, these were well resolved and were estimated to account for <10% of the total detector response. Further analyses were performed by chemical ionisation-MS (CI-MS), probe distillation EI-MS, field ionisation-MS (FIMS), and elemental analysis; yet the information provided by each was limited to a few 'average' molecular types. In view of the limitations of conventional methods of analysis, alternative methods were adopted. These utilised novel chemical and pyrolytic degradations of the UCM hydrocarbons. Chemical oxidation with Cr03 in glacial acetic acid produced reasonable yields of total recoverable material (40-80%). Furthermore, a high proportion were functionalised (>90%), and many resolved, which allowed their identification by EI and CI GC-MS. Surprisingly, the most abundant products of oxidation of hydrocarbon UCMs were straight chain monocarboxylic acids. This appeared to contradict literature consensus on UCM composition, namely a predominance of highly branched and/or cyclic hydrocarbons. However, from literature reported CrO oxidations of hydrocarbons, potential precursor compounds were proposed. These were monoalkyl substituted 'TO-branched acyclic and monocyclic alkanes for the aliphatic UCM and alkyl 'TO-branched monoaromatic hydrocarbons for the aromatic UCM. Proposed precursor UCM hydrocarbons were confirmed by synthesis and chemical oxidation under the same conditions. Thus each of the synthetic candidate UCM hydrocarbons [7-n-hexylnonadecane, 9-(2-phenylethyl)-heptadecane and 9-(2- cyc 1 ohexyl ethyl j--hep tade cane] produced n-acids on oxidation with Cr03- Further correlations were found for products of other synthetic alkanes and less abundant UCM oxidation products. For example, n-alkan-2-ones. iso alkan-2- ones, and 7-methyl--y-lactones could all be correlated with methyl substituted acyclic alkyl linkages on UCM hydrocarbons. The application of chemical oxidation to aliphatic UCMS of varied origin showed the technique has great potential for fingerprinting such samples. GC-MS analysis of a selected series of resolved product compounds (alkyl ketones, -y-methyl--y-lactones) showed good correlations for samples of the sane origin, yet distinct differences for UCHs from different sources. Biodegradation of the three candidate UCM hydrocarbons alongside acyclic isoprenoid alkanes and normal and monomethyl alkanea showed the UCM hydrocarbons were at least as resistant to microbial degradation as the isoprenoid alkanes. In this context it is therefore concluded that the candidate UCM compounds serve as good molecular models for hydrocarbon UCMs.

The occurrence of unresolved complex mixtures of hydrocarbons (UCMs) in the aliphatic fraction of marine sediments and organisms from areas impacted by petroleum hydrocarbons is well documented and widely accepted as an indication of fossil fuel contamination. In contrast, the presence of an aromatic UCM is often ignored and environmental concentrations of aromatic UCM hydrocarbons in marine biota and sediments are rarely reported. The aims of this study were to establish the quantitative significance of aromatic UCMs in environmental samples and to assess the toxicological significance of both aliphatic and aromatic UCMs. A reproducible method was developed and validated for the analysis and quantification of petroleum hydrocarbons in mussel (Mytilus edulis) tissue. Emphasis was placed upon development of a method which minimized losses of more volatile, lower molecular weight, toxicologically significant hydrocarbons, without compromising recovery of higher molecular weight compounds which are useful for source identification in environmental monitoring schemes. Analysis of mussels from a small number of U. K. coastal locations indicated that aromatic hydrocarbon UCMs may form a significant proportion (ca 20 %) of the total hydrocarbon body burden of mussels from areas contaminated with petroleum hydrocarbons. Aromatic UCM hydrocarbons were not observed in mussels from relatively uncontaminated areas but concentrations of 430 μg g'' (dry wt tissue) were measured in mussels from heavily impacted areas. Aliphatic UCM concentrations ranged from 7- 3445 μg gg' (dry wt tissue). For the purposes of toxicological studies, a low molecular weight model aliphatic UCM hydrocarbon, 4-propyloctane (4-PO) was synthesised. Two low molecular weight model aromatic hydrocarbons 7- cyclohexyltetralin and 7-cyclohexyl-l-propyltetralin were also synthesised using a modification of the Haworth synthesis. All three target compounds and synthetic intermediates were characterised by NMR, MSandIR. Exposure of M. edulis to 4-PO caused a significant reduction in mussel ciliary feeding activity indicating that 4-PO was indeed toxic as measured by this bioassay. The demonstrable narcotic activity of 4-PO is presumably related to the greater aqueous solubility of branched hydrocarbons compared with similar straight chain hydrocarbons. Further experiments investigating the effect of 4- PO over exposure periods up to 120h provided a unique and detailed insight into the relationship between concentration of toxicant in the gills of M. edulis and observed feeding rate. The established method of mussel feeding rate determination was modified in light of this relationship to produce an " improved rapid and reproducible screening technique. Both of the model aromatic UCM hydrocarbons were also found to be toxic to mussel ciliary feeding activity. This appears to be the first report of investigations into the toxicity of the aromatic UCM and suggests that previous studies have ignored an environmental burden of toxicological significance. Estimates of the tissue effective concentration (TEC50) for the model UCM hydrocarbons gave comparable values with those reported for the effect of other narcotic hydrocarbons upon mussel feeding rate, providing support for the theory that non-specific narcosis occurs at a relatively constant tissue concentration of toxicant. The demonstrated narcotic activity of each of the three model UCM hydrocarbons has extended the molecular weight range of narcotic hydrocarbons studied to date. The results presented herein suggest that a small proportion of low molecular weight aliphatic UCMs and perhaps a greater proportion of aromatic UCMs are of toxicological significance.

New methodologies have been developed for the determination of organotin and organolead compounds in environmental samples. Several high performance liquid chromatographic separations of organotin compounds have been tested and the best system (cation-exchange chromatography with methanol and a citrate buffer) employed for the determination of tributyltin (TBT), triphenyltin (TPhT), dibutyltin (DBT) and monobutyltin (MBT) in environmental samples. The coupling between high performance liquid chromatography (HPLQ and the inductively coupled plasma-mass spectrometer (ICP-MS) for this application has been modified to yield limits of detection of 0.44,0.26,1.4 and 0.23 ng. g-' as Sri for TBT, TPhT, DBT and MBT respectively. Different extraction procedures have been tested for the determination of organotin species in samples of environmental interest, such as sediments and biological materials. The values obtained for TBT, TPhT and DBT in the analysis of a mussel candidate reference material, CRM 477, have been incorporated in the certification campaign of this material. A liquid chromatographic separation for trimethyllead (TML) and triethyllead (TEL) has also been developed. Artificial rain water has been analysed for TML. The system proved to be valid for the determination of TML in this sample, even in the presence of high amounts of inorganic lead. Finally, isotope dilution analysis (IDA) was incorporated in the method. Tributyltin iodide (TBTI) and trimethyllead chloride (TMLCI), isotopically enriched in &quot;Sn and &quot;Pb, respectively, were synthesised. The mussel tissue CRM 477 was analysed with IDA-HPLC-ICPMS for TBT. As for the analysis without isotope dilution, the result obtained was incorporated in the certification campaign. The analysis with this methodology gave a better precision in the overall determination than external calibration analysis. Artificial rain water, at two different concentration levels, was analysed for TML with IDA-HPLC-ICP-MS. Better precision and accuracy was obtained for the analysis of this material with this method than when external calibration procedures were employed. IDA-HPLC-ICP-MS has proved to be a valid technique for the analysis of environmental samples. The technique simplifies the procedure, compensates for different sources of variability and, thus, the overall precision obtained in the analysis is improved compared to other calibration techniques.

Dyestuffs are widely used industrial chemicals, yet surprisingly little is known about their fate in the environment. The potential modes of transformation and removal of reactive dyes in treatment and in the environment are principally through anaerobic and aerobic biodegradation and photodegradation. The research herein describes the use of LC-MS analysis with laboratory simulations to develop a better understanding of the occurrence and fate of reactive dyes and their degradation products in the aquatic environment. One reason for the lack of information on the environmental fate of reactive dyes has been the paucity of robust analytical methods suitable for the determination of dyes in aqueous samples. Robust analytical methods were optimised to provide LC-MS and MSMS identification of degradation products. Additionally, interpretation of the MSMS spectra of known reactive dyes provided novel characteristic fragment ions indicative of the triazine reactive group of reactive dyes . Fibre reactive dyes are designed to have a degree of photostability and therefore their photodegradation behaviour has not been widely investigated. Little is known of their stability to daylight over prolonged periods of irradiation in dilute aqueous solutions and in the presence of humic substances. The kinetics of photodegradation of an anthraquinone dye (Reactive Blue H4R) and azo dye (Reactive Yellow P5G) were evaluated. The former underwent rapid and extensive degradation 01/2 1.5 h). The major products formed were identified using LC-MSMS and a photodegradation pathway proposed. By comparison, the photodegradation of the azo dye was significantly slower, 01/2 30 h). The addition of humic substancesa ppearedt o have little effect on the rate of photodegradationu nder the conditions used. The reduction of azo dyes under anaerobic treatment has been extensively studied, but the subsequent fate of the initial reduction products when exposed to air are not understood. Three relatively simple azo dyes, Amaranth, Sunset Yellow and Naphthol Blue-Black, were reduced and their autoxidation products identified by LC-MS. These were subsequently used to predict the autoxidation products of a more complex azo reactive dye: Reactive Red 3.1. Additionally, a persistent degradation product from the anaerobicaerobic treatment of Reactive Red 3.1 was identified from LC-MS data. Azo reactive dyes are generally regarded as being resistant to aerobic degradation and there are few published data regarding degradation pathways for reactive anthraquinone dyes. Pure cultures of Pseudomonas docunhae, A 9046 and A texaco and mixed bacterial consortia (semi-continuous activated sludge, SCAS) aerobic degradation of azo and anthraquinone reactive dyes was studied. Two azo dyes were degraded by pure cultures of A docunhae and A 9046, suggesting that azo dyes can be aerobically degraded given favourable conditions. The antraquinone dye was extensively degraded by SCAS and pure culture biodegradation. Metabolites were identified by LC-MS and a degradation pathway proposed.

This thesis describes a novel application of an artificial neural network and links together the two diverse disciplines of electroanalytical chemistry and information sciences. The artificial neural network is used to process data obtained from a Differential Pulse Anodic Stripping (DPAS) electroanalytical scan and produces as an output, predictions of lead concentration in samples where the concentration is less than 100 parts per billion. A comparative study of several post analysis processing techniques is presented, both traditional and neural. Through this it is demonstrated that by using a neural network, both the accuracy and the precision of the concentration predictions are increased by a factor of approximately two, over those obtained using a traditional, peak height calibration curve method. Statistical justification for these findings is provided Furthermore it is shown that, by post processing with a neural network, good quantitative predictions of heavy metal concentration may be made from instrument responses so poor that, if using tradition methods of calibration, the analytical scan would have had to be repeated. As part of the research the author has designed and built a complete computer controlled analytical instrument which provides output both to a graphical display and to the neural network. This instrument, which is fully described in the text, is operated via a mouse driven user interface written by the author.

Diss. (sammanfattning) Stockholm : Karol. inst., 2005. / Härtill 5 uppsatser.