Inhibition of benzo[a]pyrene-7,8-diol formation in vitro by complex organic mixtures.

Coal-derived complex organic mixtures [COM] with boiling points greater than or equal to 370 degrees C (greater than or equal to 700 degrees F) are known to inhibit both mouse skin tumor initiation by benzo[a]pyrene [BAP], and BAP-induced bacterial mutagenesis. We have examined the effects of 5 COM, with boiling points of 149-370 degrees C (300-700 degrees F), 370-398 degrees C (700-750 degrees F), 398-426 degrees C (750-800 degrees F), 426-454 degrees C (800-850 degrees F), and greater than 454 degrees C (greater than 850 degrees F), on both the rate and the route of BAP metabolism by rat liver homogenates in vitro. When co-metabolized in 40:1 excess with BAP, all of the COM reduced the rate of BAP metabolism. The 149-370 degrees C (300-700 degrees F) COM reduced the initial rate of BAP metabolism to 34% of the rate for BAP alone, while the four higher-boiling COM reduced it to 6.3-9.3% of the rate for BAP alone. In addition, the 2 highest-boiling COM (426-454 degrees C and greater than 454 degrees C boiling points) were found to reduce the percentage of BAP metabolized to BAP-7,8-diol, in comparison to incubations using BAP alone. The 370-398 degrees C and 398-426 degrees C COM did not alter the percentage of BAP metabolized to BAP-7,8-diol, while the 149-370 degrees C COM increased it. Both the general inhibition of BAP metabolism (by all of the COM), and the specific inhibition of BAP-7,8-diol formation (by the highest-boiling COM) may play a role in the inhibition of formation of BAP-induced skin tumors by these materials.

Correlation of nitroaromatic compounds with the mutagenic activity of coal fly ash.

Stack-collected fly-ash particles from a commercial pulverized-coal power plant were extracted with 60/40 w/w benzene-methanol to remove as much of the organic fraction as possible. The extract was sequentially fractionated on a series of high-performance liquid chromatography columns, and the Salmonella bacterial mutagenicity assay using both normal and nitroreductase-deficient strains was used to localize the most mutagenic fractions. Selected fractions were analyzed by a variety of techniques, including gas chromatography with dual-flame ionization and thermionic nitrogen-phosphorus detectors, gas chromatography-mass spectrometry, direct-probe low-resolution or low-voltage mass spectrometry, and high-resolution mass spectrometry. Mutagenicity data indicated that nitroorganic compounds were the primary mutagens in all samples submitted for chemical analysis. A series of homologous alkylated nitrophenanthrenes appear to be important mutagens in one major fraction, while alkylated nitrofluorenones appear to be the dominant mutagens in a second major fraction. No nitro compounds were identified in a third major fraction. In addition to the nitro compounds, substantial amounts of fluorenones were also found, although these are not believed to contribute to the direct-acting mutagenic activity of the samples.

Analysis of various classes of drugs by capillary supercritical fluid chromatography.

Three classes of drugs were screened for analysis feasibility by capillary column supercritical fluid chromatography. These included steroids, therapeutic antibiotic drugs, and drugs of abuse, such as cannabinoids. Supercritical fluid carbon dioxide was used as the mobile phase in conjunction with a methylpolysiloxane stationary phase capillary column and a flame ionization detector. All compounds considered were analyzed either as single component solutions, simple mixtures, or in actual complex mixtures.

Comparative chemical and biological analysis of coal tar-based therapeutic agents to other coal-derived materials.

In this study, methodologies developed for the analysis of synthetic fuel products were applied to the coal tar fractions isolated from coal tar-based pharmaceutical products. A pharmaceutical stock solution of 20% coal tar in alcohol, a 50% coal tar bath emulsion and a 4.3% coal tar shampoo were studied. The toxicology and chemical composition of the coal tar fractions isolated from these materials were compared with an industrial coal tar and with a direct-liquefaction coal liquid product. The coal tars and coal liquid product were fractionated into chemical classes by alumina column chromatography and individual components were identified and quantitated by high-resolution gas chromatography. The microbial mutagenicity of these materials was measured against S. typhimurium, TA 98. In addition, the industrial coal tar, coal-liquid product, and coal tar isolate from the 20% coal tar in alcohol solution were tested for initiating activity in an initiation/promotion mouse skin painting assay for carcinogenicity. The chemical compositions of the coal tar-based therapeutic agents, the industrial coal tar and direct-liquefaction coal liquid were similar. With the exception of the 50% bath emulsion, the microbial mutagenicity and tumor-initiating activity in mouse skin for those materials tested were also similar.

Microbial mutagenicity of isomeric two-, three-, and four-ring amino polycyclic aromatic hydrocarbons.

The isomers of various two-, three-, and four-ring amino polycyclic aromatic hydrocarbons were tested for mutagenic activity using a microbial plate incorporation test with four Salmonella typhimurium strains (TA98, TA100, TA1535, and TA1537). All compounds were assayed with an S9 metabolic activating enzyme system. The two-ring compounds were tested only with TA98. All were weakly mutagenic (1-10 rev/micrograms) except 2-aminobiphenyl, which was not mutagenic under these test conditions. All except two of the 13 fused three-ring compounds (aminofluorenes, aminoanthracenes, and aminophenanthrenes) were active frame shift mutagens; only the aminophenanthrenes were active base-pair mutagens. The potency of this group of isomeric compounds ranged from moderately (approximately 20 rev/microgram) to strongly (greater than 5,000 rev/microgram) mutagenic. As a group, the pericondensed four-ring amino compounds were the most mutagenic of the three groups tested. All of the aminofluoranthene and aminopyrene isomers showed significant mutagenic activity with TA98, TA100, and TA1537. In general, the mutagenic potency of the amino polycyclic aromatic compounds tested was highly dependent on the structural position of the amino group.

Contribution of nitropyrene to the mutagenic activity of coal fly ash.

Stack-collected coal fly ash from western low-sulfur coal was extracted with 60:40 benzene/methanol. This extract was fractionated by preparative-scale high performance liquid chromatography (HPLC) and the mutagenic activity of 14 fractions was evaluated by microbial assay with Salmonella typhimurium TA1538. A widespread distribution of direct-acting mutagens, which probably includes both mono- and dinitroaromatics, was detected. HPLC methods were also used to isolate 1-nitropyrene from the total benzene/methanol extract. The identification of 1-nitropyrene was based on gas chromatographic and HPLC retention measurements and mass spectral data. The concentration of 1-nitropyrene in the ash extract was determined by quantitative HPLC analyses. Mutagenicity assays of the total extract and an authentic 1-nitropyrene standard with Salmonella strains TA1538, TA100, and TA98 indicated that the 1-nitropyrene accounts for approximately 0.03-0.16% of the total mutagenic activity of the extract.

Identification of volatile organic compounds produced by fluorescent pseudomonads on chicken breast muscle.

Four different fluorescent pseudomonads were isolated from spoiled, uncooked chicken breasts and were grown in pure culture on initially sterile chicken breast muscle at 2 to 6 degrees C for 14 days. The volatile compounds produced by each culture were concentrated on a porous polymer precolumn and separated and identified by high-resolution gas chromatography-mass spectrometry.

Capillary column gas chromatography of environmental polycyclic aromatic compounds.

The methodologies are described for isolating clean fractions of polycyclic aromatic compounds from diverse environmental samples such as air particulate matter, sediments, and fish tissue. The common step in all procedures is the separation of the polycyclic aromatic compound fraction into well-defined chemical classes by adsorption chromatography on an alumina column. These procedures greatly facilitate the detailed characterization of the polycyclic aromatic hydrocarbons, sulfur heterocycles, and nitrogen heterocycles by capillary column gas chromatography.

Dimethyl and monomethyl sulfate: presence in coal fly ash and airborne particulate matter.

Dimethyl sulfate and its hydrolysis product monomethyl sulfate have been found at concentrations as high as 830 parts per million in fly ash and in airborne particulate matter from coal combustion processes. This discovery poses a new environmental problem because of the mutagenic and carcinogenic properties of these compounds.