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Analysis of waterborne paints by gas chromatography-mass spectrometry with a temperature-programmable pyrolyzer.

Gas chromatography-mass spectrometry (GC-MS) with a temperature-programmable pyrolyzer was used for the analysis of waterborne paints. Evolved gas analysis (EGA) profiles of the waterborne paints were obtained by this temperature-programmed pyrolysis directly coupled with MS via a deactivated metal capillary tube. The EGA profile suggested the optimal thermal desorption conditions for solvents and additives and the subsequent optimal pyrolysis temperature for the remaining polymeric material. Polymers were identified from pyrograms with the assistance of a new polymer library. The solvents were identified from the electron ionization mass spectra with the corresponding chemical ionization mass spectra. The additive was identified as zinc pyrithione by comparison with authentic standard. Zinc pyrithione cannot be analyzed by GC-MS as it is. However, the thermal decomposition products of zinc pyrithione could be detected. The information on the decomposition temperature and products was useful for the identification of the original compound.

Gas Chromatography-Mass Spectrometry↗

Analysis of complex mixtures recovered from space missions statistical approach to the study of Titan atmosphere analogues (tholins).

To study Titan, the largest moon of Saturn, laboratory simulation experiments have been performed to obtain analogues of Titan's aerosols (named tholins) using different energy sources. Tholins, which have been demonstrated to represent aerosols in Titan's haze layers, are a complex mixture, resulting from the chemical evolution of several hydrocarbons and nitriles. Their chromatographic analysis yields complex chromatograms, which require the use of mathematical procedures to extract from them all the information they contain. Two different chemometric approaches (the Fourier analysis approach and the statistical model of peak overlapping) have been successfully applied to pyrolysis-GC-MS chromatogram of a tholin sample. Fundamental information on the mixture's chemical composition (number of components, m) and on the separation system performance (separation efficiency, sigma) can be easily estimated: the excellent correspondence between the data calculated by the two independent procedures proves the reliability of the statistical approaches in characterizing a tholin chromatogram. Moreover, the plot of autocorrelation function contains, in a simplified form, all the information on the retention pattern: retention recursivities can be easily singled out and related to specific molecular structure variations. Therefore, the autocorrelation function (ACF) plot constitutes a simplified fingerprint of the pyrolysis products of tholins, which can be used as a powerful tool to characterize a tholin sample.

Aerosols↗

Thermospray liquid chromatographic-mass spectrometric analysis of mutagenic substances present in tryptophan pyrolysates.

During protein pyrolysis, as can occur when broiling meat or fish, mutagenic substances are formed, as shown by in vitro mutagenicity assays. Some of the most active compounds have been shown to originate from tryptophan (Trp). Hundreds of grams of Trp had to be used previously to study the formation of these compounds by classical separation and detection methods. Studies have been made of the formation of two active heterocyclic amines, 3-amino-1,4-dimethyl-5H-pyrido[4,3-b]indole (Trp-P-1) and 3-amino-1-methyl-5H-pyrido[4,3-b]indole (Trp-P-2), by heating Trp at different temperatures and for different periods at time. Advantage was taken of the high selectivity and sensitivity of thermospray liquid chromatography-mass spectrometry coupling, which permitted the use of much smaller amounts (10 g) of starting material. These conditions permit a more accurate control of the pyrolysis temperature and the method of extraction can be shortened and simplified. The results show that Trp-P-1 and Trp-P-2 were already formed at 250 degrees C. These substances were detectable in the low ppb range, i.e., less than the threshold levels necessary to elicit a positive response in the Ames test under standard conditions.

Animals↗

Identification of non-cross-linked compounds in methanolic extracts of cured and aged linseed oil-based paint films using gas chromatography-mass spectrometry.

Methanolic extracts of paint samples of different composition and age were qualitatively investigated by GC-MS using an on-column injector after off-line methylation or trimethylsilyl derivatisation, and on-line thermally assisted (trans)methylation with tetramethylammonium hydroxide using Curie-point pyrolysis-GC-MS. The combination of these three analytical strategies led to the identification of typical oxidation products of unsaturated fatty acids by interpretation of their mass spectrum. Some of the identified compounds have not been reported before. Both the off-line and on-line GC-MS strategy show series of short-chain fatty (di)acids and C16 and (oxidised) C18 fatty acids. The major advantage of the on-line pyrolysis-GC-MS approach is that chemical work-up is minimal and very quick. With this technique both the carboxylic acid functionalities, and hydroxyl groups are methylated. Young paint films are shown to contain relatively more oxidised C18 fatty acids and less diacids compared to older paints, which is indicative for the on-going oxidation processes within the paint. After trimethylsilylation, monoacylglycerols are detected indicative for hydrolytic processes, which reflect the relative distribution of the most prominent silylated fatty acids present. Relatively more C16 and C18 monoacylglycerols are found in young paints, whereas older paints contain higher amounts of monoacylglycerols of diacids.

Gas Chromatography-Mass Spectrometry↗

Carbon-mineral adsorbents from waste materials: case study.

Waste bleaching earth from the food industry obtained in the process of fruit juice purification was utilized for preparation of carbon-mineral adsorbents. The waste material, containing 25.8 wt% C, was subjected to three kinds of treatment: (1) direct pyrolysis at 400 degrees C with a suitable temperature program; (2) preliminary hydrothermal modification (200 degrees C, 8 h, 15.3 atm) and then pyrolysis as in method 1; (3) preliminary thermal treatment (400 degrees C) and then chemical treatment (boiling in 3% solution Na(2)CO(3)), followed by heating at 400 degrees C (10 min). Moreover, the materials obtained by these methods were subjected to additional thermal treatment at 700 degrees C with a suitable temperature program. Both the morphology and the topography of carbon deposits and, in consequence, the porous structure of the obtained adsorbents depend on the method of their preparation. The additional thermal treatment of these samples at 700 degrees C makes it possible to obtain adsorbents of more thermally stable carbon deposits possessing better parameters of the porous structure. Carbon-mineral adsorbents of different specific surface areas (S(BET) from 17.6 to 153 m(2)/g) and pore volumes (from 0.035 to 0.093 cm(3)/g) were prepared. The mechanism of phenol and p-nitrophenol adsorption on the obtained adsorbents was discussed and their properties were compared with the suitable literature data.

Journal Article↗

Molecular composition of the wall of insect olfactory sensilla-the chitin question.

Identification of chitin in sensory hairs of olfactory sensilla of silkmoths was performed using two independent methods. Firstly, ultrathin sections were labelled with gold-conjugated wheat germ agglutinin and showed positive labelling in the cuticule of sensilla as well as in the antennal cuticle. Secondly, isolated sensory hairs and body scales were subjected to analytical pyrolysis in combination with gas chromatography and mass spectrometry. Chromatograms of both sensory hairs and scales, included several pyrolysis products, which unequivocally demonstrate the contribution of chitinous moieties to the chemical composition of both types of cuticle. This study supports the notion that even the very thin cuticle of olfactory sensilla is composed of both an epi- and a true exocuticle. The carbohydrate components of the latter cuticle most probably are responsible for the extremely high resilience and breaking limit of these delicate structures.

Journal Article↗

Natural organic matter and DBP formation potential in Alaskan water supplies.

Disinfection by-products (DBP) are formed when natural organic matter (NOM) in water reacts with a disinfectant, usually chlorine. DBPs are a health risk element and regulated under the Safe Drinking Water Act. A study was conducted to evaluate the characteristics of NOM that contribute to DBPs in 17 different drinking water systems in Alaska. In order to determine the nature of the organic matter contributing to DBPs, DBP formation potential was compared with standard water quality parameters such as UV-254, color and dissolved organic carbon (DOC), as well as pyrolysis-gas chromatography/mass spectrometry (GC/MS). Results showed strong correlations between UV-254 and DBP formation potential for all waters studied. DOC, on the other hand, was less strongly correlated to DBP formation potential. Unlike previous studies, the total trihalomethane and haloacetic acid formation potentials were equal on a mass concentration basis for the waters studied. Pyrolysis-GC/MS indicated that NOM contributing to DBPs were primarily phenolic compounds. This finding was consistent with previous studies; however, unlike other studies, no correlation was found between aliphatic compounds in the raw waters and DBP formation potential.

Alaska↗

Main products and kinetics of the thermal degradation of polyamides.

The thermal degradation of the polyamides (PA) 6, 12, 66 and 612 was investigated by means of thermal analysis/mass spectrometry (TA-MS) and pyrolysis in a german standard oven. Sample masses were about 20 and 40 mg. The heating rates used in the dynamic studies were 1, 5 and 10 K min(-1). Both air and nitrogen atmospheres were utilized. The kinetic parameters were calculated from the TA-MS measurements and the main decomposition products were registered online. The evolved products from the pyrolysis oven were captured and analyzed off-line by GC/MS.

Journal Article↗

Optimising the preparation of activated carbon from digested sewage sludge and coconut husk.

Preparation of activated carbon from sewage sludge is a promising way to dispose of sewage sludge as well as to produce a low-cost adsorbent for pollutant removal. This research work aimed to optimise the condition for activated carbon preparation from anaerobically digested sewage sludge with the additive coconut husk. The sewage sludge sample was mixed with the additive coconut husk. The preparation condition variables investigated involved the concentration of the ZnCl2 solutions, heating temperature, dwell time and heating rate in pyrolysis and the mixing ratio of coconut husk to sewage sludge. Surface area, pore size distribution, aqueous phenol adsorption capacity and the production yield of the final products were determined and compared. Experimental results revealed that low concentrations of ZnCl2 solution tended to improve the microporosity of the final product. Heating temperature had a considerable impact on the surface area, pore size distribution and phenol adsorption capacity of the final products, whereas dwell time and heating rate performed comparatively insignificantly. The effect of increasing the mixing ratio of coconut husk to sewage sludge was principally to increase the microporosity of the final products. The activated carbon with the highest BET surface area was produced with the activation of 5 M ZnCl2 solution and, thereafter, pyrolysis at a heating temperature of 500 degrees C for 2 h with a heating rate of 10 degrees C/min. The mixing ratio of 1:4 in terms of coconut husk to sewage sludge based on their dried weights was found to be most cost effective.

Adsorption↗

Contribution of stack gases and solid process wastes to the organic pollutant output of thermal waste treatment plants.

Within the scope of fundamental investigations as well as individual research projects (W. Knorr, B. Hentschel, C. Marb. S. Schädel, M. Swerev, O. Vierle, J.-P. Lay, 1999. Rückstände aus der Müllverbrennung-Chancen für eine stoffliche Verwertung von Aschen und Schlacken. Initiativen zum Umweltschutz, 13 ed., Deutsche Bundesstiftung Ulmwelt, Erich Schmidt, Berlin), the Bavarian State Office for Environmental Protection performs emission measurements at thermal waste treatment plants to optimize operation, to accompany and support development of new technologies, and to study the effect of this kind of waste treatment technology on the environment. Based on recent studies (October 1995-July 1999) at six municipal solid waste incinerators (MSWI) in Bavaria all emission streams (solid and gas) are characterized with respect to organic pollutant contents and compared to the emissions of waste pyrolysis. The significant ranges of pollutant concentration as well as the specific congener patterns observed are similar for all MSWI, regardless of differences in technical design and waste input, but differ markedly from those of the pyrolysis products. The overall approach, including the sampling of all output streams and the determination of mass streams and volume flow rates, allows the calculation of the total output of different organic pollutants for waste incineration plants aand to estimate the relative contribution of each of the emission streams to the total pollutant load. Removal efficiencies are also calculated for the air pollution control (APC) systems of the different MSWI plants.

Air Movements↗

Mechanism of the formation of polychlorinated dibenzo-p-dioxins and dibenzofurans from chlorophenols in gas phase reactions

The pyrolysis of chlorinated phenates at a temperature of about 280 degrees C results in the formation of definite chlorinated dibenzodioxin (PCDD) congeners [1-3]. It is shown that in gas phase reactions chlorophenols react in the presence of oxygen above 340 degrees C not only to PCDD but also to chlorinated dibenzofurans (PCDF). The mechanism of this reaction of chlorophenols to PCDD and PCDF was elucidated. In a first step phenoxyradicals are formed which are capable of forming PCDDs and PCDFs. This is confirmed by the oxygen dependency of the reaction. In an argon atmosphere no dimerization of chlorophenols could be observed at 420 degrees C. By the identification of intermediates and by analyzing the PCDF isomers formed from individual chlorophenols the reaction pathway is elucidated. As intermediates in the formation of PCDFs polychlorinated dihydroxybiphenyls (DOHB) were identified. These are most likely formed by the dimerization of two phenoxy radicals at the hydrogen substituted carbons in ortho-positions under simultaneous movement of the hydrogen atoms to the phenolic oxygen PCDDs are formed in the gas phase via ortho-phenoxyphenols (POP) analogous to the pyrolysis of phenates, but due to the radical mechanism in the first condensation step to POPs not only a chlorine atom is capable for substitution but also the hydrogen atoms. The formation of the DOHBs and their condensation to PCDFs and hydroxylated PCDFs as well as the ratio of PCDD to PCDF formed show a strong dependency on the reaction temperature, the substitution pattern of the chlorophenols and the oxygen concentration.

Journal Article↗

Characterization by mass spectrometry of poly(3-hydroxyalkanoates) produced by Rhodospirillum rubrum from 3-hydroxyacids.

The sequence distributions of two microbial copolyesters obtained by fermentation of Rhodospirillum rubrum, grown with 3-hydroxyhexanoic or 3-hydroxyheptanoic acids, were determined by analyzing the oligomers prepared by partial pyrolysis or partial methanolysis of these copolyesters using fast atom bombardment mass spectrometry (FAB-MS). Oligomers up to pentamers were identified in the case of partial pyrolysis and up to tetradecamers in the case of partial methanolysis. The comparison between the experimental and calculated peak intensities of FAB mass spectra allows the calculation of compositions and sequence distributions, which in these copolyesters follow Bernoullian statistics, indicating that they are random terpolyesters.

Biopolymers↗

Degradation of household biowaste in reactors.

Household derived biowaste was degraded by biological methods. The system involves the combined method of low-solids (up to 10% w/v of total solids (TS)) anaerobic digestion and aerobic degradation for the recovery of energy (biogas) and the production of fine humus-like material which can be used as a soil amender or a substrate for further thermal treatment (pyrolysis, gasification). The performance of batch and continuous processes carried out in bioreactors (stirred tank reactor, air-lift) of working volume 6 and 18 dm(3), at different temperatures (25-42 degrees C) was monitored by reduction of TS, volatile solids, chemical oxygen demand, total organic carbon, C/N in time. The application of continuous process with recirculation (33%) caused that for residence time of 8-16 h the obtained degree of organic load reduction was similar to that obtained after 72-96 h of the batch process. The experimental data of batch aerobic degradation was also subjected to kinetic analysis. The sequence of the two processes: aerobic and anaerobic or anaerobic and aerobic showed that the degree of organic load reduction was similar in both cases, while the amount of produced biogas was four times higher when the first stage was anaerobic. The final product after dewatering was subjected to pyrolysis and gasification. The gases obtained were characterised by a high heat of combustion of about 11-15 MJ Nm(-3).

Aerobiosis↗

The effect of tobacco ingredients on smoke chemistry. Part I: Flavourings and additives.

The effects of 450 tobacco ingredients added to tobacco on the forty-four "Hoffmann analytes" in mainstream cigarette smoke have been determined. These analytes are believed by regulatory authorities in the USA and Canada to be relevant to smoking-related diseases. They are based on lists published by D. Hoffmann and co-workers of the American Health Foundation in New York. The ingredients comprised 431 flavours, 1 flavour/solvent, 1 solvent, 7 preservatives, 5 binders, 2 humectants, 2 process aids and 1 filler. The cigarettes containing mixtures of the ingredients were smoked using the standard ISO smoking machine conditions. The levels of the "Hoffmann analytes" in the smoke from the test cigarettes containing the ingredient mixture were compared to those from control cigarettes without the ingredients. In practice, flavouring ingredients are typically added to tobacco that also contains casing ingredients and reconstituted tobacco materials. In order to keep the tobacco mixtures as authentic as possible, three comparisons have been made in this study. These are: (a) control cigarette containing a typical US blended, cased tobacco incorporating reconstituted tobacco versus test cigarettes that had flavouring ingredients added to this tobacco; (b) control cigarette containing tobacco only versus test cigarettes with the tobacco cased and incorporating flavourings; (c) control cigarette containing tobacco only versus test cigarette incorporating additives made in an experimental sheet material. The significances of differences between the test and control cigarettes were determined using both the variability of the data on the specific occasion of the measurement, and also taking into account the long-term variability of the analytical measurements over the one-year period in which analyses were determined in the present study. This long-term variability was determined by measuring the levels of the 44 "Hoffmann analytes" in a reference cigarette on many occasions over the one-year period of this study. The ingredients were added to the experimental cigarettes at or above the maximum levels used commercially by British American Tobacco. The effect of the ingredient mixtures on total particulate matter and carbon monoxide levels in smoke was not significantly different to the control in most cases, and was never more than 10% with any ingredient mixture. It was found that, in most cases, the mixtures of flavouring ingredients (generally added in parts per million levels) had no statistically significant effect on the analyte smoke yields relative to the control cigarette. Occasionally with some of the mixtures, both increases and decreases were observed for some smoke analyte levels relative to the control cigarette. These differences were generally up to about 15% with the mixtures containing flavouring ingredients. The significance of many of the differences was not present when the long-term variability of the analytical methodology was taken into account. For the test cigarettes with ingredient mixtures containing casing ingredients, there were again no significant changes in smoke analyte levels in most cases. Those changes that were observed are as follows. Decreases in smoke levels were observed with some ingredient mixtures for most of the tobacco specific nitrosamines (up to 24%), NO(x), most of the phenols (up to 34%), benzo[a]pyrene, and some of the aromatic amines and miscellaneous organic compounds on the "Hoffmann list". Increases were observed for some test cigarettes in smoke ammonia, HCN, formaldehyde and lead levels (up to 24%). The significance of the ammonia and lead increases was not present when the long-term variability of the analytical methodology was taken into account. The yields of some carbonyl compounds in smoke were increased in one comparison with an additives mixture containing cellulosic components; in particular, formaldehyde was increased by 68%. This was the largest single change seen in any smoke analyte level in this study. These carbonyls are produced from the pyrolysis of cellulosnyls are produced from the pyrolysis of cellulosic and other polysaccharide materials, present in the additives mixture. With this test cigarette, all tobacco specific nitrosamines, phenols, semi-volatile bases, NO(x) and some aromatic amines and miscellaneous organic compounds on the "Hoffmann list" were decreased, by up to 22%. The significance of many of these differences remained even when the long-term variability of the analytical methodology was taken into account. The levels of all other "Hoffmann analytes" in the smoke were not significantly different to those of the control cigarette. With the exception of the determinations of "tar", nicotine and carbon monoxide, there are currently no internationally recognised standard methods for measurement of the other "Hoffmann analytes". Each laboratory uses its own methods and there are large laboratory-to-laboratory variations, as well as variations over time in a given laboratory. Therefore, it is important that in any comparison of smoke analytes amongst different cigarettes, all the analytes should be measured in the same laboratory and at the same time. This was the case in the present study and all the methods have been validated internally.

Ammonia↗

Synthesis and characterization of catalysts produced from paper mill sludge. I. Determination Of NOx removal capability.

Characteristics and catalytic properties of a series of carbon-based catalysts (CBCs) produced from paper mill sludge were evaluated. The major processes involved in the production of the catalysts were chemical activation, impregnation, pyrolysis, and post pyrolysis rinsing. The porous structure, catalytic activity and thermostability of the catalysts were tailored during the production stage by introducing hetero-atoms (zinc chloride, and ferric nitrate) in the carbon structure. Characterization of the produced CBCs included determination of the surface area, pore size, and pore size distribution (PSD) from standard N2-adsorption isotherm data. The extent of graphitization and the presence of metal crystals were identified from X-ray diffraction (XRD). The limit of the catalyst gasification was estimated from thermogravimetric analysis (TGA) conducted in an oxidized environment. The NOx reduction capability of the produced catalysts was evaluated in the presence of carbon monoxide using a fixed bed reactor. The reaction temperature ranged from 300 to 500 degrees C. It was shown that paper mill sludge is an excellent precursor for the production of CBCs with NOx removal capability of 66-94%. The catalytic capability of the produced CBCs varied according to the method of production, catalyst surface properties (surface area, pore structure, PSD), metal composition and reaction temperature. The highest NOx removal capacity was observed for the catalytic reactions carried out at 400 degrees C. The mesoporous catalyst produced with a Zn:Fe molar ratio of 1:0.5 exhibited the maximum NOx removal catalytic activity of 94%.

Carbon↗

Soluble polycyclic aromatic hydrocarbons in raw coals.

Polycyclic aromatic hydrocarbons (PAHs) are considered to be a group of compounds that pose potential health hazards since some PAHs are known carcinogens. During coal utilization processes, such as coal combustion and pyrolysis, PAHs released may be divided into two categories according to their formation pathways. One category is derived from complex chemical reactions and the other is from free PAHs transferred from the original coals. PAHs released from complex chemical reactions during combustion and pyrolysis have received considerable attention in recent years. However, free PAHs contained in raw coals have not been seriously considered as a source of these materials to be released during the utilization of coal. The goal of this study was to observe the relation between the content of PAHs in different coals and the elemental composition of the coals. In this study, eight bituminous coals with dry, ash-free carbon values varying from 65% to 90% were selected. Each coal was extracted with dichloromethane in a Soxhlet extractor for 6 h. The extracts were quantitatively analyzed with a gas chromatograph/mass spectrometer (GC-MS). More than 20 kinds of PAHs were identified. The total amount of PAHs determined varied from 1.2 to 28.3 mg/kg from the various coal types. The maximum total PAHs extracted was reached when the carbon content exceeded 84% by weight.

Anthracenes↗

Effect of gas-containing microspheres and echo contrast agents on free radical formation by ultrasound.

Stabilized microbubbles (microspheres) are widely used to enhance the contrast of ultrasound imaging. Our data provide direct evidence that the contrast agents, Levovist, PVC-AN (polyvinylidene chloride-acrylonitryl copolymer), and Albunex (compared to 5% human albumin), at concentrations comparable to those used for ultrasound imaging, enhance H2O2 production (through the superoxide-dependent pathway) in air-saturated aqueous solutions exposed to 47 kHz ultrasound above the cavitation threshold. These agents also act as scavengers of .H atoms and .OH radicals, thus lowering H2O2 formation (by recombination of .OH radicals) in argon-saturated solutions. EPR spin trapping also reveals that secondary radicals derived from the contrast agents are produced by reactions with .H and .OH which are formed by pyrolysis of water inside cavitation bubbles. In addition, the contrast agents themselves undergo pyrolysis reactions in the cavitation bubbles as demonstrated by formation of methyl radicals. Possible deleterious consequences of the formation of sonochemical intermediates may have to be assessed, particularly since some of the echo contrast agents have been shown to lower the cavitation threshold of diagnostic ultrasound. Unlike the microspheres formed from organic molecules, inorganic microspheres, Eccospheres, because of their stability and inert nature with respect to participation in free radical processes, appear to be suitable tools for enhancing the yields of aqueous sonochemical reactions.

Acrylic Resins↗

Direct detection and quantitation of He@C60 by ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry.

In this paper, we report negative ion microelectrospray Fourier-transform ion cyclotron resonance (FT-ICR) mass spectrometry of C60 samples containing approximately 1% 3He@C60 or 4He@C60. Resolving He@C60- and 4He@C60- from C60 containing 3 or 4 13C instead of 12C atoms is technically challenging, because the target species are present in low relative abundance and are very close in mass. Nevertheless, we achieve baseline resolution of 3He@C60- from 13C3(12C57-) and 4He@C60- from 13C4(12C56-) in single-scan mass spectra obtained in broadband mode without preisolation of the ions of interest. The results constitute the first direct mass spectrometric observation of endohedral helium in a fullerene sample at this (low) level of incorporation. The results also demonstrate the feasibility of determining the extent of He incorporation from the FT-ICR mass spectral peak heights. The present measurements are in agreement with those obtained by the pyrolysis method [1-3]. Although limited in sensitivity, the mass spectral method is faster and easier than pyrolysis.

Journal Article↗