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We examined the biological reactivity in vitro of nanoparticles of organic compounds (NOC) with diameters, d = 1-3 nm, a class of combustion-generated particulate relatively unstudied compared to larger more graphitic soot particles because of their small size even though they may contribute significantly to the organic fraction of PM sampled from vehicle exhausts and urban atmospheres. We tested NOC samples collected from 2004 model vehicle emissions and laboratory flames. NOC produced a dose dependent mutagenic response in Salmonella bacteria, suggesting that NOC may add significantly to the overall mutagenicity of vehicle emissions. Incubation with peptides caused agglomeration and precipitate of the otherwise stable NOC suspension, but the chemical and/or physical nature of the NOC-peptide interactions could not be resolved. A significant cytotoxic response was measured above a critical dose of NOC in mouse embryo fibroblasts NIH3T3 cells along with possible evidence of cellular uptake by optical and confocal microscopy. The toxicological assays showed that NOC collected from flames and vehicle exhausts effectively interacted in vitro with both prokaryotic and eukaryotic cells. Differences in mutagenic potencies observed for various Salmonella strains with and without metabolic activation indicate differences in the chemical composition of NOC collected from different vehicles and flames.

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RESUMEN

UV-visible extinction and scattering and two extra situ sampling techniques: atomic force microscopy (AFM) and differential mobility analysis (DMA) are used to follow the evolution of the particles formed in flames. These particle sizing techniques were chosen because of their sensitivity to detect inception particles, which have diameters, d<5 nm, too small to be observed with typical particle measurement instrumentation. The size of the particles determined by AFM and DMA compares well with the size determined by in situ optical measurements, indicating that the interpretation of the UV-visible optical signal is quite good, and strongly showing the presence of d=2-4 nm particles. UV-visible extinction measurements are also used to determine the concentration of d=2-4 nm particles at the exhausts of practical combustion systems. A numerical model, able to reproduce the experimentally observed low coagulation rate of nanoparticles with respect to soot particles, is used to investigate the operating conditions in the combustion chamber and exhaust system for which 2-4 nm particles survive the exhaust or grow to larger sizes. Combustion generated nanoparticles are suspected to affect human and environmental health because of their affinity for water, small size, low rate of coagulation, and large surface area/weight ratio. The ability to isolate nanoparticles from soot particles in hydrosols collected from combustion may be useful for future analysis by a variety of techniques and toxicological assays.

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A systematic comparison of spectra obtained with extra and in situ diagnostics in the soot preinception region of rich, premixed ethylene air flames suggests that combustion generated organic carbon (OC) particulate can be extracted from flames and isolated from other flame material for further chemical analysis. Both the trend with height above the burner and the form of UV fluorescence and absorption spectra from extra situ sampled material captured in water agree with those measured in situ. These results show that the OC particulate formed in flames is partially water soluble. However, the collection efficiency can be increased using less polar solvents, like acetonitrile and dichloromethane. The fluorescence spectra from the water samples are comprised both a naphthalene-like component and a broad band UV fluorescence component similar to that observed in situ which is attributed to flame generated OC particulate. The broad band UV fluorescence centered around 320 nm is also observed very early in flames and does not change considerably with increasing flame residence time. These results support previous hypotheses that the UV broad band fluorescence is from carbonaceous material comprised two-ring aromatics, formed earlier than soot in the flame, and is still present along with soot at higher heights or flame residence times.

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We demonstrate the full resolution of isotope shifts in atomic O by means of sub-Doppler laser optogalvanic spectroscopy of (18)O-enriched samples. The measurements are performed to within a few percent accuracy on four transitions ranging from 605 to 646 nm and involving excited states. Previously published values from conventional spectroscopy are either unavailable or are one order of magnitude less accurate and in marginal agreement with our data.