G. Grimmer

Profile of the polycyclic aromatic compounds from crude oils

Zusammenfassung8 Rohöle unterschiedlicher Provenienz wurden auf ihren Gehalt an polycyclischen aromatischen Kohlenwasserstoffen, deren isosteren Sauerstoff- (Furane) und Schwefelanaloga (Thiophene) sowie an Carbazolen mit Hilfe der Glas-Capillar-Gas-Chromatographie quantitativ untersucht. Am Beispiel eines Rohöls (Qatar) wurden 226 verschiedene Verbindungen entweder durch Vergleich der Retentionszeiten und Massenspektren mit denen von Referenzsubstanzen identifiziert oder, wo diese nicht vorhanden waren, massenspektrometrisch als polycyclische aromatische Verbindungen (PAC) charakterisiert. Der PAC-Gehalt (>3 Ringe) der untersuchten Öle schwankt innerhalb einer Zehnerpotenz. Der relative Gehalt an schwefelhaltigen PAC (S-PAC) ist mit dem Gesamtschwefelgehalt linear korrelierbar.SummaryEight crude oils of different origin were quantitatively analysed in respect to the content of polycyclic aromatic hydrocarbons, isosteric oxygen (furans) and sulphur (thiophenes) analogues, and carbazoles by means of glass-capillary gas-chromatography. From a crude oil (Qatar) 226 different compounds were either identified by comparing their retention times and mass spectra with those of reference materials, or where these are lacking characterized as polycyclic aromatic compounds (PAC) by mass spectrometry. The PAC-content (>3 rings) of these crude oils investigated ranged within one order of magnitude. The relative content of sulphur containing PAC can be correlated to the total sulphur content.

Profile of the polycyclic aromatic hydrocarbons from lubricating oils inventory by GCGC/MS — PAH in environmental materials, part 1

ZusammenfassungEine Schmierölprobe wurde auf ihren Gehalt an polycyclischen aromatischen Kohlenwasserstoffen (= PAH), Thiophen- und Furanhaltigen polycyclischen aromatischen Verbindungen (S-PAC und O-PAC) untersucht. Diejenigen Verbindungen, deren Gehalt über 0,02 mg/kg lag, wurden durch Vergleich mit Originalsubstanzen identifiziert oder — wenn Referenzsubstanzen nicht zur Verfügung standen — massenspektrometrisch charakterisiert. Diese Bestandsaufnahme wurde mit einer GC-MS-Kombination durchgeführt. Die Massenspektren von typischen Vertretern einiger Stoffklassen (S-PAC, O-PAC und Methylderivate) wurden diskutiert.Die Profile der im Mineralöl enthaltenen polycyclischen aromatischen Verbindungen (= PAC) sind von den PAC-Profilen der durch unvollständige Verbrennung oder Pyrolyse entstandenen deutlich verschieden.Um einen Überblick über den Konzentrationsbereich der PAC in verschiedenen nicht gebrauchten Motoren-Schmierölen zu bekommen, wurden 22 Handelsmuster auf ihren Gehalt an 14 ausgewählten PAC untersucht.SummaryPolycyclic aromatic hydrocarbons (= PAH), sulphur containing and oxygen containing polycyclic aromatic compounds (= S-resp. O-PAC) which occur in concentrations higher than 0.02 mg/kg in a lubricating oil sample were identified by comparison with reference substances (34) or, if reference compounds are lacking, characterized by mass spectrometry (58 compounds). Glass capillary gas chromatography combined with mass spectrometry was used for this inventory. Mass spectra of typical individuals from several classes (S-PAC, O-PAC, and methyl-derivatives) are discussed in detail.The profile of polycyclic aromatic compounds (= PAC) contained in mineral oils is significantly different from that obtained by incomplete combustion or pyrolysis of organic materials.To get a survey of the range of PAC-concentration in different engine oils, 22 commercial samples have been examined for a selected number of PAC.

Gaschromatographic determination of polycyclic aromatic hydrocarbons, aza-arenes, aromatic amines in the particle and vapor phase of mainstream and sidestream smoke of cigarettes

The present arrangement collects particles and semivolatiles of main- and sidestream smoke and allows a recovery of the trapped substances nearly quantitatively and without impurities. The fractionation procedure allows to separate various groups of carcinogens such as PAH, aza-arenes and aromatic amines for analytical and biological studies. Sidestream smoke contains ten times more polycyclic aromatic hydrocarbons (PAH) compared with mainstream smoke. This holds also true for aza-arenes and amines. PAH of the gaseous phases include only 1% of the particle-bound PAH.

Sedimentary record of heavy metals and polycyclic aromatic hydrocarbons in Lake Constance.

The enrichment of heavy metals and polycyclic aromatic hydrocarbons (PAH) in dated sediments from Lake Constance during the past 75 years corresponds to the general increase of European coal consumption within the same period of time. Coals are assumed to be the main source of heavy-metal enrichment; incomplete combustion (pyrolysis) of coal also seems to be responsible for the very sharp increase of PAH.

Biomonitoring of polycyclic aromatic hydrocarbons in highly exposed coke plant workers by measurement of urinary phenanthrene and pyrene metabolites (phenols and dihydrodiols)

SummaryA filter combination consisting of an impregnated glass fibre and a control filter was used for the collection of air samples in which gaseous and particulate polycyclic aromatic hydrocarbons (PAHs) were determined. To estimate the loss of lower boiling PAHs, d10-phenanthrene was applied as internal standard. A simple, well-reproducible method for the determination of 1-, 2-, 3-, 4- and 9-hydroxyphenanthrene, 1,2-, 3,4- and 9,10 dihydroxydihydrophenanthrene, 1-hydroxypyrene and 1,2-dihydroxy-1,2-dihydropyrene is described. By means of personal air samplers the exposure to PAHs of four coke plant employees working at different locations was measured over 4 days. Simultaneously the 24-h urine was collected and stored frozen until analysed. The main excretion product of pyrene is a 1-hydroxypyrene conjugate, whereas phenanthrene is excreted predominantly as dihydrodiol conjugate. As expected, workers on the battery topside were exposed the most and accordingly excreted by far the highest amounts of PAHs. Up to 34.0 μg phenanthrol conjugates (total of all isomeric phenols) and 195.5 μg dihydrodiol conjugates (total of all isomeric dihydrodiols) were excreted in the 24-h urine (mean of 4 days). The metabolite profiles of five isomeric phenanthrene phenols and three isomeric dihydrodiols exhibited only small percentage variations within one individual whereas significant interindividual differences were observed. These findings may indicate a genetically determined enzyme pattern responsible for the metabolic conversion of PAHs.

Quantification of the carcinogenic effect of polycyclic aromatic hydrocarbons in used engine oil by topical application onto the skin of mice

SummaryThe purpose of this investigation was to identify the substances mainly responsible for the carcinogenic effect of used engine oil from gasoline engines using topical application as a carcinogen-specific bioassay. This was performed by comparison of the tumorigenic effect of single fractions with that of an unseparated sample of the lubricating oil.The probit analysis of the results shows:1)The used engine oil, from gasoline-driven automobiles, investigated provoked local tumors after long-term application to the dorsal skin of mice. The incidence of carcinoma depended on the dose of the oil.2)The fraction of the polycyclic aromatic hydrocarbons (PAH) containing more than three rings accounts for about 70% of the total carcinogenicity in the case of crankcase oil. This fraction constitutes only up to 1.14% by weight of the total oil sample.3)The content of benzo(a)pyrene (216.8 mg/kg) accounts for 18% of the total carcinogenicity of the used oil.4)Regarding the reduced carcinogenicity of the oil sample, which was reconstituted from all fractions, it seems possible that some of the carcinogenic substances were lost due to volatility, with evaporation of the solvents from the oil-fractionation processes.5)Regarding the small effect of the PAH-free fraction, as well as the equal carcinogenic effects of the PAH-fraction (containing more than three rings) and the reconstituted oil sample, no hints for a co-carcinogenic activity were obtained.

Determination of polycyclic aromatic hydrocarbons, azaarenes, and thiaarenes emitted from coal-fired residential furnaces by gas chromatography/mass spectrometry

ZusammenfassungDa die krebserzeugende Wirkung von Emissionen aus Steinkohlebrikett-beheizten Zimmeröfen nahezu vollständig durch die im Kondensat enthaltenene polycyclischen aromatischen Verbindungen (PAC) mit mehr als 3 Ringen verursacht wird, wurde die Zusammensetzung dieser PAC-Fraktion untersucht.Mehr als 170 neutrale [111 polycyclische aromatische Kohlenwasserstoffe (PAH), 57 Thiaarene, 6 Oxaarene] sowie 70 basische Verbindungen (Azaarene) konnten mit der GC/MS-Kombination als PAC charakterisiert werden (Nachweisgrenze 0,1 mg/kg Brikett). Etwa 80 Verbindungen wurden durch den Vergleich mit Referenzsubstanzen identifiziert. Um in einigen zweifelhaften Fällen die Identität der isolierten mit der synthetischen Verbindung zu bestätigen, wurden bei 11 PAH mit einem Molgewicht von 302 zusätzlich auch UV- und Fluorescenzspektren verglichen [Naphtho(1,2-k)fluoranthen, Dibenz(e,k)acephenanthrylen, Naphth(2,3-e)acephenanthrylen, Naphtho(2,3-k)fluoranthen, Dibenzo(de,qr)naphthacen, Coronen, Dibenzo(fg,op)naphthacen, Naphtho(1,2,3,4-def)chrysen, Benzo(b)perylen, Dibenzo(def,j)chrysen, Benzo(rst)pentaphen]. Diese Verbindungen sind von besonderem Interesse, da PAC mit 6 und mehr Ringen im Tierversuch etwa 50% der carcinogenen Wirkung des Steinkohlenbrikett-Emissionskondensates verursachen.SummarySince the carcinogenic effect of emissions from hard coal briquet-fired furnaces is almost entirely caused by polycyclic aromatic compounds (PAC) with more than three rings, the composition of this fraction has been analyzed in detail.More than 170 neutral [111 polycyclic aromatic hydrocarbons (PAH), 57 thiaarenes, 6 oxaarenes] and 70 basic (azaarenes) compounds were characterized as PAC by means of GC/MS (limit of detection 0.1 mg/kg briquet). About 80 compounds were identified by comparison with reference standards. In order to obtain unequivocal evidence for the identification of 11 PAH with a molecular weight of 302, the UV- and fluorescence spectra were compared with those of the synthesized reference compounds [naphtho(1,2-k) fluoranthene, dibenz(e,k)acephenanthrylene, naphth-(2,3e) acephenanthrylene, naphtho(2,3-k)fluoranthene, dibenzo (de,qr)naphthacene, coronene, dibenzo(fg,op)naphthacene, naphtho(1,2,3,4-def)chrysene, benzo(b)perylene, dibenzo (-def,j)chrysene, benzo(rst)pentaphene]. In case of the emission condensate from hard coal briquets, PAC containing 6 and more rings cause about 50% of the carcinogenic effect in animal experiments.

Detection of carcinogenic aromatic amines in the urine of non-smokers.

Smoking is thought to be one of the most important anthropogenic risk factors involved in the development of urinary bladder cancer in humans. Tobacco smoke contains a complex mixture of chemicals including potent carcinogens such as aromatic amines. In the present study the amounts of several freebase aromatic amines including the potent carcinogens 2-aminonaphthalene and 4-aminobiphenyl have been analyzed in the urine of 48 German urban living smokers and non-smokers. The results indicate that (i) both groups excrete the identical set of four aromatic amines; (ii) smokers excrete approximately twice the total amount of these amines, but similar amounts of 2-aminonaphthalene and 4-aminobiphenyl are found in non-smokers; and (iii) the excreted aromatic amines are decomposed in the urine within a few hours thus, explaining why aromatic amines are difficult to detect in this matrix. Their decomposition could be prevented by adding small amounts of p-toluidine to the freshly collected urine. Unlike smokers the origin of aromatic amines detected in the urine of non-smokers is at present unknown. Based on the cotinine levels found in the urine of non-smokers environmental tobacco smoke can be excluded as a major source of aromatic amines. In addition, neither diesel exhaust-related nitroarenes nor the corresponding amino-derivatives, to which they may be metabolically converted, were found. The detected urinary levels of aromatic amines arising from sources other than tobacco smoke or diesel exhaust may play a role in the bladder cancer etiology of non-smokers.

Bestimmung des Gesamtgehaltes aller polycyclischen aromatischen Kohlenwasserstoffe in Luftstaub und Kraftfahrzeugabgas mit der Capillar-Gas-Chromatographie

A method of enrichment and separation of polycylic aromatic hydrocarbons [anthracene, phenanthrene, fluoranthene, pyrene, benzo(a)fluorene, benzo(b)fluorene, benzo(c)fluorene, benzo(c)phenanthrene, benzo(ghi)fluoranthene, benzo(a)anthracene, chrysene, triphenylene, benzo(b)fluoranthene, benzo(j)fluoranthene, benzo(e)pyrene, benzo(a)pyrene, perylene, dibenz(a,j)anthracene, dibenz(a,h)anthracene, benzo(ghi)perylene, anthanthrene, coronene] by capillary-GLC is described. The amount of polycylic aromatic hydrocarbons is determined by comparison of FID-signals in relation to standards. Automobile exhaust and air pollutants demonstrate different relations of benzo(a)-pyrene to anthanthrene, benzo(ghi)perylene, and coronene.ZusammenfassungEs wird ein Anreicherungsverfahren und die capillar-gas-chromatographische Bestimmung von polycyclischen aromatischen Kohlenwasserstoffen beschrieben. Zur quantitativen Auswertung werden die Flächen der F.I.D.-Signale mit zwei inneren Standards verglichen. Kraftfahrzeugabgas und Luftstaub aus Industriegebieten unterscheiden sich durch charakteristische Mengenrelationen von Benzo(a)pyren zu Anthanthren, Benzo(ghi)perylen und Coronen.

PROFILE ANALYSIS OF POLYCYCLIC AROMATIC HYDROCARBONS AND METAL CONTENT IN SEDIMENT LAYERS OF A LAKE

The question is investigated whether polycyclic aromatic hydrocarbons (PAH) in the annual sediment layers of a lake mainly result from air dust pollution. Sample layers taken from drilling cores going back to 1915 show no significant differences at the forest shore (no buildings) during this period. In contrast, samples taken from a built-up area of the shore (with a highway and a main railway line) show today 5 times the amount of PAH compared with 1915. The same trend is observed in the content of Zn, whereas Pb, Fe, Cr, Ni, Cu and Mn levels are constant. Identification or characterization of PAH was accomplished by comparison of the retention times and mass spectrometry of authentic compounds. Sixty-four PAH are described. The results indicate that the burden of carcinogenic PAH air pollutants has increased 5-fold from 1915-1970.