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For the purpose of fire analysis and fire safety engineering, the development of empirical correlations for major species yields in compartment fires has become an important priority due to the inability to calculate these quantities from first principles. Studies of simplified upper layer environments have shown that major species production rates can be correlated with the equivalence ratio in what is known as the Global Equivalence Ratio concept (GER). Due to the simplification in these past experiments, it was not known if the GER concept was valid for compartment fires. Therefore, there was a need to determine if correlations existed between major species yields and the equivalence ratio for actual compartment fires. Since the flow of toxic gases from a room poses a hazard to building occupants, it was also important to determine if correlations for CO yield outside of a compartment on fire exist, particularly when external burning occurs. A 2.2 m³ test compartment was used to investigate the burning of four fuels (hexane, PMMA, spruce and flexible polyurethane foam) in compartment fires. The test compartment was specially designed with a two-ventilation path system which allowed the direct measurement of the plume equivalence ratio (the ratio of the fuel volatilization rate to the air entrainment rate normalized by the stoichiometric fuel-to-air ratio). Empirical correlations between the upper layer yield of major species and the plume equivalence ratio were shown to exist The results reveal that the production of CO is primarily dependent on the compartment flow dynamics (i.e., the equivalence ratio) and upper layer temperature. A chemical kinetics study indicated that increased compartment temperature affects upper layer species yields in two ways 1) the generation of species in the plume is changed and 2} oxidation of post-flame gases in the layer is affected. The correlations developed in the compartment fifes were qualitatively similar to those developed by Beyler for simplified upper layer environments. However, quantitative differences existed and are explained by the temperature effect. The species yields downstream of hexane compartment flues were investigated and compared to upper layer yields. Results showed that downstream CO yields can be correlated to the plume equivalence ratio when taking into account the occurrence of external burning. When sustained external buning occurred for equivalence ratios greater than 1.7, downstream CO yields were reduced to 10 to 25 percent of the upper layer value. Results are very encouraging in indicating that an ignition criterion based on lean flammability limits is useful in predicting the flammability of upper layer gases in compartment fires. An ignition index value of 1.3 indicated the occurrence of sustained external burning and, thus, a reduction of CO, for the hexane fires studied. / Ph. D.

The goal of this project was to determine the feasibility of non-invasively monitoring the blood gases of construction workers for carbon monoxide exposure via pulse oximetry. In particular, this study sought to understand the impact of motion artifacts caused by the worker's activities and to determine if those activities would prevent the blood gas sensor from detecting the onset of carbon monoxide poisoning. This feasibility study was conducted using a blood oxygen sensor rather than a blood carbon monoxide sensor for several reasons. First, blood gas sensors that measure blood carbon monoxide are not readily available in suitable physical form factors. Second, sensors for blood oxygen and blood carbon monoxide operate on the same physical principles and thus will be affected in the same way by worker motions. Finally, using a blood oxygen sensor allowed the study to be conducted without exposing the human subjects to carbon monoxide. A user study was conducted to determine the distribution of motion artifacts that would be created during a typical work day. By comparing that distribution to a worst-case estimate of time to impairment, the probability that helmet will adequately monitor the worker can be established. The results of the study show that the helmet will provide a measurement capable of warning the user of on setting carbon monoxide poisoning with a probability greater than 99%. / Master of Science

published_or_final_version / Environmental Management / Master / Master of Science in Environmental Management

In this work the magnesium, zinc, nickel and cobalt MOFs of the MOF-74 isostructural family are used to probe metal-dependent adsorbate interactions with water and with carbon monoxide because of their ability to generate open metal sites upon activation. An isostructural family is used so that the only variable from one MOF to another is the metal incorporated into the framework. For water adsorption isotherms with humidities up to 90%, the observed trend at 298K and 1 bar is Mg-MOF-74 > Zn-MOF-74 > Co-MOF-74 > Ni-MOF-74. This observed trend is due to Lewis acid-base interactions. When the weight effect is removed, differences are still observed, especially below 40% relative humidity, thereby confirming that there is a metal effect. These studies revealed that PXRD alone cannot indicate the level of structural decomposition and that none of the four isostructures fully retain their structural integrity on exposure to humidified air because of microstrain and/or the presence of oxygen; more studies examining the extent of structural decomposition need to be undertaken. For carbon monoxide adsorption the general observed trend for P < 4 bar and temperatures of 298, 313 and 333K is Co-MOF-74 > Ni-MOF-74 > Zn-MOF-74 > Mg-MOF-74. This trend is based on π-backbonding interactions. Here again, differences remain after removal of the weight effect, confirming the metal dependence. Notably, Co-MOF-74 has the highest CO loading at 298K and 1 bar reported so far. Both the Toth and Virial Isotherms were used to fit the CO adsorption data followed by the use of the Clausius-Clapeyron equation to find the isosteric heats of adsorption, qst. The results from the Toth isotherm are more reliable and showed that qst remains constant as loading increases for Mg-MOF-74, decreases for Zn-MOF-74 and increases with loading for Co-MOF-74 and Ni-MOF-74; Ni-MOF-74 had the highest heat of adsorption at all loadings. It appears that using the Clausius-Clapeyron equation to calculate qst is an inappropriate method for Ni-MOF-74 so other methods such as calorimetry are recommended. It is also recommended to model the data of all the MOFs with other isotherm models such as Sips equation and to investigate the possibility of chemisorption for the cobalt and nickel isostructures. Finally, Henry’s constant results reveal that Ni-MOF-74 has the highest affinity for CO at low coverages.

Diss. (sammanfattning) Stockholm : Karol inst., 2004. / Härtill 5 uppsatser.

D.Phil. (Geography) / The Infrared Atmospheric Sounding Interferometer (lASI), operational in polar-orbit since 2006 on the European MetOp-A satellite, is the most advanced of its kind in space. It has been designed to provide soundings of the troposphere and lower stratosphere at nadir in a spectral interval of 0.25 em" across the range 645-2 760 em". Fine spectral sampling such as this is imperative in the sounding of trace gases. Since its launch, the routine retrievals of greenhouse, species from IASI measurements have made a valuable contribution to atmospheric chemistry studies at a global scale. The main contribution of this thesis is the development of a new trace gas retrieval scheme for IASI measurements. The goal was to improve on the global operational scheme in terms of the algorithm complexity, speed of calculation and spatial resolution achieved in the final solution. This schemedirectly retrieves column integrated trace gas densities at single field-of-view (FOV) from IASI measurements within a 10% accuracy limit. The scheme is built on the Bayesian framework of probability and based on the assumption that the inversion of total column values, as apposed to gas profiles, is a near-linear problem. Performance of the retrieval scheme is demonstrated on simulated noisy measurements for carbon monoxide (CO). Being a linear solution, the scheme is'highly dependent on the accuracy of the a priori. A statistical estimate of the a priori was computed using a principal component regression analysis with 50 eigenvectors. The corresponding root-mean-square (RMS) error of the a priori was calculated to be 9.3%. In general terms, the physical retrieval improved on the a priori, and sensitivity studies were performed to demonstrate the accuracy and stability of the retrieval scheme under a numberof perturbations. A full system characterization and error analysis is additionally preformed to elicidate the nature of this complex problem. The hyperspectral IASI measurements introduce a significant correlation error in the retrieval. The Absorption Line Cluster (ALC) channel selection method was developed in this thesis, to address the correlation error explicitly. When a first neighbour correlation factor of 0.71 is assumed in the measurement error covariance for the clusters of ALC channels, then most of the correlation error is removed in the retrieval. In conclusion, the total column trace gas retrieval scheme developed here is fast, simple, intuitive, transparent and robust. These characteristics together make it highly suitable for implementation in an operational environment intended for air quality monitoring on a regional scale.

Despite the reputation of carbon monoxide (CO) as a silent killer, new evidence suggests that this gaseous molecule has anti-inflammatory, anti-cancer and vasoprotective properties. Unfortunately, little is known about the role of CO in the body. However, proteins present in mitochondria are believed to be important targets. We previously synthesized a class of novel and structurally modifiable flavonol-based CO-releasing molecules (CORMs). Flavonols are commonly found in fruits and vegetables. The base structure, Flav-1, is fluorescent, exhibits low toxicity, and releases CO after exposure to visible light. Previous reports indicate that addition of a triphenylphosphonium (TPP) tail allows chemical structures to enter mitochondria. We hypothesized that addition of a TPP tail of two or eight carbons in length to Flav-1 (Mito-Flav-C2 or -C8) would facilitate targeting of mitochondria, and thus, localized light-induced CO release. Toxicity of these TPP-tailed molecules was determined in human umbilical vein endothelial cells (HUVECs) and lung epithelial carcinoma cells (A549), using standard cell viability assays. Evaluation of toxicity using the MTT assay revealed lower toxicity of Flav-1 in HUVECs compared to A549 cells, but addition of the TPP tails increased toxicity in both cell lines. However, unlike the MTT assay, Flav-1 with and without tails had similar toxicity when measured in HUVECs by the lactate dehydrogenase assay. Photo-degradation experiments were performed by exposing cells until their light emission was undetectable by using lasers in the near-UV and within the visible light spectrum. Localization of the compounds was observed using a confocal microscope by co-staining with MitoTracker Red (MTR) and Hoechst to visualize the mitochondria and nucleus, respectively. Fluorescence microscopy images of cells treated with Mito-Flav-C2 or -C8 revealed an increase in uptake, compared to Flav-1, plus co-localization with MTR, which suggests mitochondrial localization. A549 cells exposed to laser light or a full spectrum of light lost all fluorescence of Mito-Flav-C2, which indicates CO release. This work highlights the successful synthesis of the first mitochondria targeting CORMs, and that CO release is achievable using different light sources. Moreover, these TPP-tailed CORMs will allow for controlled and localized release of CO to further study its physiological targets.

During the last two years, the electricity prices in Sweden have risen due to unstable weather conditions, recovery from the COVID-19 pandemic and limited access to electricity. This has led to people finding alternative ways of heating up their residences, e.g., fireplace. The Swedish Medical Products Agency found an increase in carbon monoxide poisoning related to residential heating during 2022, which gave the topic a boost in the news and media. The aim for the study was to investigate the knowledge about carbon monoxide poisoning among Swedish house owners, and to see if there was a correlation between electricity prices and number of cases carbon monoxide poisoning in Sweden during the period 2008-2021. A paper- and web survey was conducted and sent out to 480 Swedish houseowners, selected by Postnord. Electricity prices and cases of carbon monoxide poisoning was received from the internet via Statistics Sweden and the Swedish National Board of Health and Welfare. Regarding the questions covered in this study, house owners' knowledge varied. Recognition of the symptoms and prevalence of carbon monoxide poisoning was known by most of the respondents, whilst course of action in case of intoxication was not as well known. A weak positive correlation was shown between electricity prices and number of cases carbon monoxide poisoning. The increase in electricity prices and the number of cases carbon monoxide poisoning during the 2020s, would make it interesting to do further investigation.

The behavior of adsorbed carbon monoxide on platinum was studied using potential difference infrared spectroscopy. Three solvents and three electrolytes were chosen, and data gathered at both high and low adsorbate coverages. The rate of change of IR peak position with applied potential, the Stark tuning rate, was used as an indicator of the local electric field strength at the interface. It was determined that neither solvated cation size nor bulk dielectric constant accounts for the changes in Stark tuning rate with different solvents. / Master of Science