Flame retardants are substances, which addition in various materials (furniture, plastics, electronics equipment, textiles, etc) could save a lot of lives and injuries caused by fires. On the other side, the migration of flame retardants from products during their whole life cycle results in their ubiquitous presence in the environment and reflects negative effects on ecosystems and human health. Global consumption of organophosphate flame retardants (OFR) as alternative substitutes of polybrominated diphenyl ethers has increased sharply in recent years. Studies on the presence and sources of OFR in surface water, ground water, sediments, snow, rainwater, indoor and outdoor air and analyses of OFR in these compartments have also increased in the last decade. In this doctoral thesis an analytical method was developed to determine six OFR (tris(2-chloroethyl) phosphate (TCEP), tris(2-chlorisopropyl) phosphate (TCPP), tris(1,3-dichloro-2-propyl) phosphate (TDCP), tris(2-butoxyethyl) phosphate (TBEP), tri(n-butyl) phosphate (TnBP) and triphenyl phosphate (TPP)) in soil. The method consists of a combination of Twisselmann extraction and solid-phase microextraction (SPME), followed by gas chromatography-mass spectrometry (GC-MS). To develop the method, spiked soils were extracted using a Twisselmann extractor after freeze-drying. The extracts were evaporated to dryness, redissolved, and filtered. A volume of 7 mL was then analysed by SPME, followed by GC-MS. The effects of different parameters on analyte recoveries during sample preparation e.g. solvent for Twisselmann extraction, solvent for redissolving the extract, addition of copper, and filtration of the extract were systematically investigated. Under optimum conditions, 10 g of soil were extracted using toluene, and the extract was redissolved in methanol/water (1:14) and filtered. It was not necessary to add copper. For TnBP, TBEP, TCPP, and TCEP, recoveries ranged from 77.0 % to 89.6 %. Those for TPP and TDCP were much lower, at 31.5 % and 42.0 %, respectively (addition level 22.9-45.8 ng/g). The variability of recoveries under these conditions was between 0.3 and 16.2 % (n = 3). Limits of detection (LOD) were 0.002-3 ng/g. When ultrasonication was used instead of Twisselmann extraction in the developed method, recoveries were three to four times lower (27.4 % to 30.6 %), but the variability of recoveries was below 3 % (n = 3). The method was applied to quantify OFR in soils collected from different sampling locations (urban, semi-urban and rural) in Germany. The results indicated for the first time that atmospheric deposition leads to soil contamination by OFR. Since it has been shown in animal experiments (F344/N rats and B6C3F1 mice) that chlorinated OFR were carcinogen and also have negative effects on human health (Matthews et al., 1991, 1993, Johnson, 1999), the further studies were focused on sources of chlorinated OFR. Therefore, the influence of dry and wet deposition processes as a source of chlorinated OFR in soils was systematically investigated. Soil samples were collected in 2010/11 during a period of snow falling to snow melting, a period of rainfall and a dry period. Snow and rainwater samples were also collected from the soil sampling site. Concentrations of TCEP were between 236 and 353 ng/L in snow and 78 and 234 ng/L in rain. TCPP concentrations were between 226 and 284 ng/L in snow and 371 and 385 ng/L in rain. In soil samples, concentrations ranged from 5.07 to 23.48 ng/g dry weight (dwt) for TCEP and 5.66 to 19.82 ng/g dwt for TCPP. Concentrations of TDCP in rainwater and snow samples were rather low (46 and 100 ng/L, respectively); concentrations of TDCP were below the limit of detection in soil samples. Snow melting caused enhanced soil concentrations of TCEP and TCPP. However a greater effect of snow melting was observed for TCEP than for TCPP. No significant correlation between precipitation amounts and soil concentrations was observed for both compounds. The influence of wet deposition to the soil contents of TCEP and TCPP may be covered by volatilisation or by the migration of both compounds to deeper soil zones with seepage water, based on their volatility and high water solubility, respectively. Snow was found to be even a more efficient source of chlorinated OFR in soil than rainwater. During dry weather, the soil concentrations of both compounds seemed to be driven mainly by concentrations in air, which are driven by source emission strengths and photochemical degradation in the atmosphere. Rainwater concentrations of OFR were used to assess air concentrations from the scavenging ratios at equilibrium conditions and the potential for the accumulation of OFR in soil based on the air-soil exchange was estimated. Calculated values of median air concentrations were 0.0034 ng/m3 for TCEP and 0.99 ng/m3 for TCPP. Total OFR specific loads were 3756 ng m-2 day-1 within the first 24 hours and 3028 ng m-2 day-1 within the next 24 h. Fugacity calculations (0.011 to 0.103 for TCPP and 0.005 to 0.073 for TCEP) indicated net deposition from air to soil for both compounds.

Global consumption of organophosphate esters (OPs), which are used as flame retardants and plasticizers, is rapidly increasing. Their use as additives in diverse applications poses a risk as they may be emitted from the products they are added to and be further transported in the environment. Therefore, the levels, distribution, and possible sources of 15 OPs, some of which are reported to be toxic, were investigated in indoor and outdoor environments. An exposure assessment was performed, and the exposure to OPs via inhalation was examined for five occupational groups. In addition, based on the findings of the studies, the total flow of OPs in Sweden was estimated. In indoor environments, the OPs detected in air and dust varied between the sites, but generally reflected the building materials, furniture etc. used in the premises. A majority of the analysed OPs were detected in all samples, and public buildings tended to have higher levels than domestic buildings. The chlorinated OPs dominated in indoor air and wipe samples from vehicles. They were also abundant in the dust samples. Some occupational groups were significantly more exposed to OPs than others. Aircraft technicians, for example, were exposed to about 500 times more tributyl phosphate than day care centre personnel. Upon domestic and industrial cleaning, OPs are discharged with the wastewater via the sewage system to sewage treatment plants (STPs). Irrespective of the size of the STPs investigated, they had similar levels of OPs in their influents, indicating that products containing OPs are widely used by the communities they serve. In some cases, it was possible to trace elevated levels of individual OPs to specific sources. The OPs were poorly removed from the wastewater, and the chlorinated OPs especially tended to pass through the STPs without being removed or degraded. Thus, levels of OPs in their effluents were also similar, as were the levels in their sludge. Of the total amounts of OPs entering the STPs, 50% was emitted to the recipients via the effluent. Hence, there is room for significant improvement in the treatment processes. Carps living in a pond, receiving STP effluent were found to contain relatively high levels of OPs compared to perch collected in lakes from background locations. Air and road traffic were also identified as sources of OPs: the concentration of total OPs in snow samples decreased with increasing distance from a major road intersection, and OPs were detected in aircraft lubricants and hydraulic fluids and in waste oil from cars and lorries. OPs are emitted from both diffuse and direct sources to the environment and may then be spread by long-range air transport, rivers and streams. This probably explains why OPs were also detected in air and fish from background locations. Finally, OPs are ubiquitous substances in both indoor and outdoor environments. The possibility that prolonged exposure to OPs at the levels found may cause adverse effects, for instance in aqueous organisms, cannot be excluded. For example, the OP levels in snow were of the same magnitude as reported effect concentrations. Similarly, in some premises, indoor exposure to OPs was close to the suggested guideline value. However, since these studies include only a limited number of samples, and data regarding the health and environmental effects of OPs are sparse, no definitive conclusions regarding their possible environmental effects can be drawn. / Den globala konsumtionen av organiska fosfatestrar (OP) för användning som flamskyddsmedel och mjukgörare har ökat kraftigt på senare tid. Det breda användningsområdet för dessa additiv medför en risk att de kan avges från de produkter de är satta till och transporteras vidare ut i miljön. Följaktligen undersöktes källor till, halter av, och fördelning i inom- och utomhusmiljöer av 15 OP, varav en del har toxiska effekter. Vidare har exponering för OP i bl.a bostäder och offentliga byggnader beräknats. Utöver detta undersöktes exponeringen för OP via inandning hos 5 yrkesgrupper. Slutligen användes resultaten för att uppskatta det totala flödet av OP i Sverige. I de olika inomhusmiljöerna uppmättes ett flertal OP i varierande halter i damm och luft, men generellt speglade halterna byggnadsmaterial, möbler etc. som fanns i lokalerna. De offentliga lokalerna tenderade att uppvisa högre halter än privata hus, förmodligen beroende på högre brandskyddskrav. Klorerade OP dominerade i inomhusluft samt i avstrykningsprov från fordon och förekom även i höga halter i damm. Vissa yrkesgrupper var exponerade för betydligt högre halter OP än andra, t.ex. exponerades flygtekniker för upp till 500 ggr högre lufthalter av tributylfosfat jämfört med förskollärare. I samband med våtskurning i inomhusmiljöer (hushåll, industrilokaler, osv.) släpps avsevärda mängder OP ut i avloppet och når till sist reningsverk. Oberoende av storlek på reningsverken var halterna av OP relativt lika, i vardera ingående vatten och slam, vilket indikerar en bred användning av OP i samhället. I vissa fall kunde specifika källor till OP i avloppsvattnet spåras. Exempelvis hade två av reningsverken högre halter av en klorerad OP jämfört med övriga reningsverk. Dessa behandlade vatten från en skumplastfabrik, respektive en fabrik som tillverkar flamskyddad färg. Avskiljningsgraden av OP från avloppsvatten visade sig generellt vara dålig, i synnerhet klorerade OP tenderade att passera genom reningsverken utan att degraderas eller avskiljas från vattnet. Av den mängd OP som nådde reningsverken släpptes 50 % ut till miljön via utflödet. Som ett resultat av detta uppvisade karpar från en damm påverkad av utflödet från ett reningsverk höga halter OP jämfört med abborrar från referenssjöar. Det finns därför anledning att förbättra tekniken på reningsverken. Flyg- och vägtrafik kunde också identifieras som källor till OP i miljön. OP uppmättes i hydrauloljor och smörjmedel för flygplan samt i spillolja från bilar och lastbilar. Vidare minskade totalhalten OP i snöprov med ökat avstånd från en större vägkorsning. OP släpps således ut från både diffusa och direkta källor och kan sedan spridas vidare via luft och vattendrag. Därmed var det inte förvånande att OP även påträffades i luft och fisk från bakgrundslokaler. Avslutningsvis förekommer OP i varierande halter i såväl inom- som utomhusmiljöer. Det kan inte uteslutas att långvarig exponering för de halter av OP som uppmätts skulle kunna orsaka negativa effekter hos t.ex vatten- eller jordlevande organismer. I smälta snöprov från en flygplats uppmättes exempelvis halter av OP i samma storleksordning som rapporterade effektkoncentrationer. Dessutom visade sig den beräknade exponeringen av OP, i några av de provtagna inomhuslokalerna, uppgå till halter nära det föreslagna riktvärdet för OP i Tyskland. Dessa studier inkluderar dock ett begränsat antal prov och provtyper och kunskapen om dessa föreningars miljö- och hälsoeffekter är bristfällig. Därför bedöms underlaget som för litet för att några definitiva slutsatser ska kunna dras angående OPs eventuella effekter på miljön.

Orientador: Leonardo de Souza Mendes / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Elétrica e de Computação / Made available in DSpace on 2018-08-21T21:10:42Z (GMT). No. of bitstreams: 1 Nunes_FabioPessoa_M.pdf: 6956532 bytes, checksum: 55194ac0a721f75279923f8424903edc (MD5) Previous issue date: 2012 / Resumo: O resumo poderá ser visualizado no texto completo da tese digital / Abstract: The abstract is available with the full electronic document / Mestrado / Telecomunicações e Telemática / Mestre em Engenharia Elétrica

An investigation into the performance of several combined gas-steam power generating plants’ cycles was undertaken at the School of Engineering and Technology at the University of Hertfordshire and it is predominantly analytical in nature. The investigation covered in principle the aspect of the fundamentals and the performance parameters of the following cycles: gas turbine, steam turbine, ammonia-water, partial oxidation and the absorption chiller. Complete thermal analysis of the individual cycles was undertaken initially. Subsequently, these were linked to generate a comprehensive computer model which was employed to predict the performance and characteristics of the optimized combination. The developed model was run using various input parameters to test the performance of the cycle’s combination with respect to the combined cycle’s efficiency, power output, specific fuel consumption and the temperature of the stack gases. In addition, the impact of the optimized cycles on the generation of CO2 and NOX was also investigated. This research goes over the thermal power stations of which most of the world electrical energy is currently generated by. Through which, to meet the increase in the electricity consumption and the environmental pollution associated with its production as well as the limitation of the natural hydrocarbon resources necessitated. By making use of the progressive increase of high temperature gases in recent decades, the advent of high temperature material and the use of large compression ratios and generating electricity from high temperature of gas turbine discharge, which is otherwise lost to the environment, a better electrical power is generated by such plant, which depends on a variety of influencing factors. This thesis deals with an investigation undertaken to optimize the performance of the combined Brayton-Rankine power cycles' performance. This work includes a comprehensive review of the previous work reported in the literature on the combined cycles is presented. An evaluation of the performance of combined cycle power plant and its enhancements is detailed to provide: A full understanding of the operational behaviour of the combined power plants, and demonstration of the relevance between power generations and environmental impact. A basic analytical model was constructed for the combined gas (Brayton) and the steam (Rankine) and used in a parametric study to reveal the optimization parameters, and its results were discussed. The role of the parameters of each cycle on the overall performance of the combined power cycle is revealed by assessing the effect of the operating parameters in each individual cycle on the performance of the CCPP. P impacts on the environment were assessed through changes in the fuel consumption and the temperature of stack gases. A comprehensive and detailed analytical model was created for the operation of hypothetical combined cycle power and power plant. Details of the operation of each component in the cycle was modelled and integrated in the overall all combined cycle/plant operation. The cycle/plant simulation and matching as well as the modelling results and their analysis were presented. Two advanced configurations of gas turbine cycle for the combined cycle power plants are selected, investigated, modelled and optimized as a part of combined cycle power plant. Both configurations work on fuel rich combustion, therefore, the combustor model for rich fuel atmosphere was established. Additionally, models were created for the other components of the turbine which work on the same gases. Another model was created for the components of two configurations of ammonia water mixture (kalina) cycle. As integrated to the combined cycle power plant, the optimization strategy considered for these configurations is for them to be powered by the exhaust gases from either the gas turbine or the gases leaving the Rankine boiler (HRSG). This included ChGT regarding its performance and its environmental characteristics. The previously considered combined configuration is integrated by as single and double effect configurations of an ammonia water absorption cooling system (AWACS) for compressor inlet air cooling. Both were investigated and designed for optimizing the triple combination power cycle described above. During this research, tens of functions were constructed using VBA to look up tables linked to either estimating fluids' thermodynamic properties, or to determine a number of parameters regarding the performance of several components. New and very interesting results were obtained, which show the impact of the input parameters of the individual cycles on the performance parameters of a certain combined plant’s cycle. The optimized parameters are of a great practical influence on the application and running condition of the real combined plants. Such influence manifested itself in higher rate of heat recovery, higher combined plant thermal efficiency from those of the individual plants, less harmful emission, better fuel economy and higher power output. Lastly, it could be claimed that various concluding remarks drawn from the current study could help to improve the understanding of the behaviour of the combined cycle and help power plant designers to reduce the time, effort and cost of prototyping.