Pollutant emissions during the pyrolysis and combustion of flexible polyurethane foam

Thermal decomposition of flexible polyurethane foam (FPUF) was studied under nitrogen and air atmospheres at 550 °C and 850 °C using a laboratory scale reactor to analyse the evolved products. Ammonia, hydrogen cyanide and nitrile compounds were obtained in high yields in pyrolysis at the lower temperature, whereas at 850 °C polycyclic aromatic hydrocarbons (PAHs) and other semivolatile compounds, especially compounds containing nitrogen (benzonitrile, aniline, quinolone and indene) were the most abundant products. Different behaviour was observed in the evolution of polychlorodibenzo-p-dioxins and furans (PCDD/Fs) at 550 °C and 850 °C. At 550 °C, the less chlorinated congeners, mainly PCDF, were more abundant. Contrarily, at 850 °C the most chlorinated PCDD were dominant. In addition, the total yields of PCDD/Fs in the pyrolysis and combustion runs at 850 °C were low and quite similar.

Introduction to the nitrofurans /

Bibliography: p. 43.

Enantioselective chemoenzymatic synthesis of 3-hydroxytetrahydrofurans

The research described in this thesis is concerned with the synthesis and stereoselective transformations of 4,5-dihydro-3(2H)-furanones and their 3-hydroxy derivatives. In Chapter 1, a review of synthetic routes to 3-hydroxytetrahydrofurans is presented. This incorporates the wide range of applications for these types of compounds. Preparative routes to and stereoselective transformations of the furanones investigated in this study are discussed in Chapter 2. The bulk of the work centers on stereoselective carbonyl group reductions to generate the 3-hydroxytetrahydrofuran derivatives in racemic form followed by kinetic resolution via lipase mediated esterification, resulting in enantioenriched 3-acetoxy and 3-hydroxytetrahydrofuran derivatives. In many cases, these processes proceed in a highly enantioselective manner. The influence of the lipase species and concentration of enzyme employed on the yield and stereochemical outcome of the reactions is examined in detail. Access to the complementary series of furanone and hydroxytetrahydrofuran derivatives by oxidation or reduction of the enantioenriched compounds was achieved through conventional synthetic methods. Chapter 2 also contains details of a novel synthetic route to a range of 2,3,5-trisubstituted furans from α-hydroxyenones and 4,5-dihydro-3(2H)-furanones. The mechanistic rationale for these transformations and the migratory aptitude of alkyl groups towards the formation of these furans is discussed in detail. Finally, Chapter 2 outlines the synthesis of a series of diarylcyclopentenones that were synthesised as part of our investigations. Chapter 3 contains a description of the synthetic procedures and biotransformations carried out together with key analytical and spectroscopic properties of the compounds studied and where appropriate, their analysis using chiral HPLC analysis.

Organic geochemistry of sediments from sapropel 94 of ODP Hole 161-974C

Analysis of the molecular composition of the organic matter (OM) from whole sediment samples can avoid analytical bias that might result from isolation of components from the sediment matrix, but has its own analytical challenges. We evaluated the use of GC * GC-ToFMS to analyze the pyrolysis products of six whole sediment samples obtained from above, within and below a 1 million year old OM-rich Mediterranean sapropel layer. We found differences in pyrolysis products furans and alkyl aromatics in the pyrolysates of sapropel samples relative to the marls confirm better preservation of marine OM in the sapropels. In addition, the presence of greater amounts of thiophenes in the sapropels than in the marls is consistent with the existence of euxinic conditions during sapropel deposition. The combination of whole sediment pyrolysis and GC × GC-ToFMS is promising, but the procedure requires careful selection of its multiple analytical variables, particularly the pyrolysis temperature and the operational features of the GC columns.

Geochemistry of the water column of southern lake Baikal during 1967-2005

At present, when the influence of human economic activity is progressively increasing, significant attention is devoted to the state of water ecosystems. All researchers engaged in these problems agree that the state of the water system (pollution and eutrophication) can only be estimated on the basis of long-term researches. Systemic monitoring (at least once per month) of ionic components (Ca2+, Mg2+, Na+, K+, bicarbonates, sulfates, and chlorides) in unfiltered water of Lake Baikal and its tributaries had been carried out under the supervision of Votintsev since 1947. Based on the analysis of systematic data on trophic components obtained during 1965-2005, we tried to estimate the present-day trophic status of the pelagic zone in the lake, define the trend of long-term changes of trophic components and understand the reasons of the distortion of cyclicity in the development of spring diatom algae, which create a favorable environment in any water basin. It should be noted that the station near Cape Polovinnyi is located 20 km away from the town of Baikal'sk. Wastewaters of the Baikal'sk pulp and paper mill is the main source of dioxins and furans in Baikal. Based on the significant difference between sulfate contents in wastewaters of the plant (>300 mg/l), tributaries of Baikal (7.5 mg/l), and waters in the southern part of the lake (3.9 mg/l), we defined the following periods: (i) period of natural seasonal patterns until 1967-1968 (prior to putting the Baikal'sk Mill into operation; (ii) period of weak anthropogenic pollution (1969-1985); and (iii) period of strong anthropogenic pollution since 1986.

Preparação e caracterização de catalisadores à base de titânio suportado em MCM-41 para produção de compostos oxigenados através da pirólise catalítica do capim elefante

In recent years, the area of advanced materials has been considerably, especially when it comes to materials for industrial use, such as is the case with structured porosity of catalysts suitable for catalytic processes. The use of catalysts combined with the fast pyrolysis process is an alternative to the oxygenate production of high added value, because, in addition to increasing the yield and quality of products, allows you to manipulate the selectivity to a product of interest, and therefore allows greater control over the characteristics of the final product. Based on these arguments, in this work were prepared titanium catalysts supported on MCM-41 for use in catalytic pyrolysis of biomass, called elephant grass. The reactions of pyrolysis of biomass were performed in a micro pyrolyzer, Py-5200, coupled to GC / MS, the company CDS Corporation, headquartered in the United States. The catalysts Ti-MCM-41 in different molar ratios were characterized by XRD, TG / DTG, FT-IR, SEM, XRF, UV-visible adsorption of nitrogen and the distribution of particle diameter and specific surface area measurement by the BET method. From the catalytic tests it was observed that the catalysts synthesized showed good results for the pyrolysis reaction.The main products were obtained a higher yield of aldehydes, ketones and furan. It was observed that the best reactivity is a direct function of the ratio Si/Ti, nature and concentration of the active species on mesoporous supports. Among the catalysts Ti-MCM-41 (molar ratio Si / Ti = 25 and 50), the ratio Si / Ti = 25 (400 ° C and 600 ° C) favored the cracking of oxygenates such as acids , aldehydes, ketones, furans and esters. Already the sample ratio Si / Ti = 50 had the highest yield of aromatic oxygenates

Growth and symbiosis of plants with arbuscular mycorrhizal fungi in soil submitted to biochar application.

Arbuscular mycorrhizal fungi (AMF), which is intrinsically present or may be introduced in soils by inoculation, is an example of natural and renewable resource to increase plant nutrient uptake. This kind of fungi produces structures (hyphae, arbuscles and sometimes vesicles) inside the plant root cortex. This mutualistic relationship promotes plant gains in terms of water and nutrient absorption (mainly phosphorus). Biochar can benefit plant interaction with AMF, however, it can contain potentially toxic compounds such as heavy metals and organic compounds (e.g. dioxins, furans and polycyclic aromatic hydrocarbons), depending on the feedstock and pyrolysis conditions, which may damage organisms. For these reasons, the present work will approach the impacts of biochar application on soil attributes, AMF-plant symbiosis and its responses in plant growth and phosphorus uptake. Eucalyptus biochar produced at high temperatures increases sorghum growth; symbiosis with AMF; and enhances spore germination. Enhanced plant growth in the presence of high temperature biochar and AMF is a response of root branching stimulated by an additive effect between biochar characteristics and root colonization. Biochar obtained at low temperature reduces AMF spore germination; however it does not affect plant growth and symbiosis in soil.

Characterization of the volatile profile of Brazilian Merlot wines through comprehensive two dimensional gas chromatography time-of-flight mass spectrometric detection.

Wine aroma is an important characteristic and may be related to certain specific parameters, such as raw material and production process. The complexity of Merlot wine aroma was considered suitable for comprehensive two-dimensional gas chromatography (GCGC), as this technique offers superior performance when compared to one-dimensional gas chromatography (1D-GC). The profile of volatile compounds of Merlot wine was, for the first time, qualitatively analyzed by HS-SPME-GCxGC with a time-of-flight mass spectrometric detector (TOFMS), resulting in 179 compounds tentatively identified by comparison of experimental GCxGC retention indices and mass spectra with literature 1D-GC data and 155 compounds tentatively identified only by mass spectra comparison. A set of GCGC experimental retention indices was also, for the first time, presented for a specific inverse set of columns. Esters were present in higher number (94), followed by alcohols (80), ketones (29), acids (29), aldehydes (23), terpenes (23), lactones (16), furans (14), sulfur compounds (9), phenols (7), pyrroles (5), C13-norisoprenoids (3), and pyrans (2). GCxGC/TOFMS parameters were improved and optimal conditions were: a polar (polyethylene glycol)/medium polar (50% phenyl 50% dimethyl arylene siloxane) column set, oven temperature offset of 10ºC, 7 s as modulation period and 1.4 s of hot pulse duration. Co-elutions came up to 138 compounds in 1D and some of them were resolved in 2D. Among the coeluted compounds, thirty-three volatiles co-eluted in both 1D and 2D and their tentative identification was possible only due to spectral deconvolution. Some compounds that might have important contribution to aroma notes were included in these superimposed peaks. Structurally organized distribution of compounds in the 2D space was observed for esters, aldehydes and ketones, alcohols, thiols, lactones, acids and also inside subgroups, as occurred with esters and alcohols. The Fischer Ratio was useful for establishing the analytes responsible for the main differences between Merlot and non-Merlot wines. Differentiation among Merlot wines and wines of other grape varieties were mainly perceived through the following components: ethyl dodecanoate, 1-hexanol, ethyl nonanoate, ethyl hexanoate, ethyl decanoate, dehydro-2-methyl-3(2H)thiophenone, 3-methyl butanoic acid, ethyl tetradecanoate, methyl octanoate, 1,4 butanediol, and 6-methyloctan-1-ol.