International studies to compare methods for personal sampling of bitumen fumes.

A newly recommended Institute of Occupational Medicine (IOM) sampler, optimized for the inhalable fraction, was compared with 'total particulate' samplers currently used by five laboratories in different countries for the analysis of bitumen fumes. Using a laboratory fume generator, all samplers were uniformly exposed to bitumen fumes from typical USA bitumen (commercial Pen 65). The results show that, for laboratory-generated bitumen fumes, benzene-extractable inhalable particulate data for the IOM sampler are consistent with benzene soluble matter data from the other samplers. Direct comparison of the IOM sampler with the 37 mm closed-face cassette (USA sampler) using an identical protocol in a single laboratory gave a ratio of 1.05:1 (USA:IOM). Similarly, for total particulate matter, the standard previously recommended by the American Conference of Governmental Industrial Hygienists (ACGIH), an average value of approximately 1 between the IOM and the five samplers was obtained. For unadulterated bitumen fumes, the geometry of the cassettes does not appear to affect entry of the particles into the sampler. Field studies may show differences in results as other factors, e.g. wind and its effect on sampling efficiency, and also particulates originating from sources other than bitumen, such as dust, are involved. These will require thorough investigation prior to the assessment of the impact of the new sampler and prior to any reconsideration of occupational exposure limits taking into account practical feasibility. Other tests were conducted on the bitumen fume samples including total organic matter, simulated distillation and polycyclic aromatic compound analysis. These additional tests were performed on the fume collected on the filter plus the volatile portion that passed through the filter and was captured on various adsorbent materials. Protocols for sample collection and analysis varied in different countries with results reflective of these differences, suggesting the need for standardization.

Formation of DNA adducts from oil-derived products analyzed by 32P-HPLC.

The aim of this study was to investigate the genotoxic potential of DNA adducts and to compare DNA adduct levels and patterns in petroleum vacuum distillates, coal tar distillate, bitumen fume condensates, and related substances that have a wide range of boiling temperatures. An in vitro assay was used for DNA adduct analysis with human and rat S-9 liver extract metabolic activation followed by 32P-postlabeling and 32P-high-performance liquid chromatography (32p-HPLC). For petroleum distillates originating from one crude oil there was a correlation between in vitro DNA adduct formation and mutagenic index, which showed an increase with a distillation temperature of 250 degrees C and a peak around a distillation point of approximately 400 degrees C. At higher temperatures, the genotoxicity (DNA adducts and mutagenicity) rapidly declined to very low levels. Different petroleum products showed a more than 100-fold range in DNA adduct formation, with severely hydrotreated base oil and bitumen fume condensates being lowest. Coal tar distillates showed ten times higher levels of DNA adduct formation than the most potent petroleum distillate. A clustered DNA adduct pattern was seen over a wide distillation range after metabolic activation with liver extracts of rat or human origin. These clusters were eluted in a region where alkylated aromatic hydrocarbons could be expected. The DNA adduct patterns were similar for base oil and bitumen fume condensates, whereas coal tar distillates had a wider retention time range of the DNA adducts formed. Reference substances were tested in the same in vitro assay. Two- and three-ringed nonalkylated aromatics were rather low in genotoxicity, but some of the three- to four-ringed alkylated aromatics were very potent inducers of DNA adducts. Compounds with an amino functional group showed a 270-fold higher level of DNA adduct formation than the same structures with a nitro functional group. The most potent DNA adduct inducers of the 16 substances tested were, in increasing order, 9,10-dimethylanthracene, 7,12-dimethylbenz[a]anthracene and 9-vinylanthracene. Metabolic activation with human and rat liver extracts gave rise to the same DNA adduct clusters. When bioactivation with material from different human individuals was used, there was a significant correlation between the CYP 1A1 activity and the capacity to form DNA adducts. This pattern was also confirmed using the CYP 1A1 inhibitor ellipticine. The 32P-HPLC method was shown to be sensitive and reproducible, and it had the capacity to separate DNA adduct-forming substances when applied to a great variety of petroleum products.

Ivermectin residues in the edible tissues of swine and cattle: effect of cooking and toxicological evaluation.

Young male pigs (25-40 kg bw) were treated experimentally with a single 0.4 mg/kg bw, s.c. dose of ivermectin (Ivomec vet. inj., MSD). The disappearance of the drug from the edible tissues 7-21 days after treatment was studied using a sensitive high-performance liquid chromatographic method. The highest residue levels were found at the injection site (up to 59 and 2.6 mg/kg 7 and 14 days post-injection, respectively). Among the other tissues studied, the residue levels 7 days post-injection showed the following order: liver (less than or equal to 50 micrograms/kg) greater than kidney (less than or equal to 25 micrograms/kg) greater than muscle (less than or equal to 20 micrograms/kg). After 21 days only traces of ivermectin (less than or equal to 2 micrograms/kg) could be detected in the muscle and other edible tissues, including the injection site. Similar residue concentrations were found in slaughterhouse material from sows therapeutically treated with ivermectin for parasite infestation. An ordinary culinary preparation of the minced beef muscle from a bull treated with ivermectin resulted in a 45% (boiling) or 50% (frying) decrease in the drug residue. Based on the known toxic effects of the drug and the results of the present and other residue studies, the suggested withdrawal time for Ivomec in edible tissues of swine and cattle is 21 and 28 days, respectively.

Dietary citric acid enhances absorption of aluminum in antacids.

Ten healthy men ingested, twice daily between meals, during each of the seven-day experimental periods: (a) citric acid (as lemon juice), (b) Al(OH)3, or (c) Al(OH)3 + citric acid. Whole blood sampled after each dietary period was analyzed electrothermally after digestion with nitric acid. Moderate, but significant, increases in mean Al concentrations as compared with pretreatment values [5 (SD 3) micrograms of Al per liter] were seen after ingestion of either citric acid or Al(OH)3: 9 (SD 4) and 12 (SD 3) micrograms/L, respectively. Ingestion of both Al(OH)3 and citric acid resulted in a more pronounced, highly significant (p less than 0.001) increase in Al concentrations, to 23 (SD 2) micrograms Al/L, probably owing to formation and absorption of Al-citrate complexes.

Gas chromatographic determination of clopidol in chicken tissues.

A method has been developed for the determination of clopidol residues in chicken tissues. After extraction and cleanup, clopidol is esterified in a 2-phase system to clopidol propionate, which is determined by gas chromatography. The 2-phase system includes, in addition to the clopidol dissolved in methanol, aqueous borax solution, hexane, propionic anhydride, and pyridine. Use of these reagents precludes the use of explosive or carcinogenic chemicals in the derivatization step, and the method is therefore suitable for routine laboratory analysis. Levels of 0.5 ppb clopidol in tissue can be determined.

Tissue residues of clopidol (3,5-dichloro-2,6-dimethyl-4-pyridinol) in chickens in relation to withdrawal times.

Broiler chickens were fed on a commercial diet containing 0.0125% clopidol for 34 days. They were killed 0-10 days after withdrawal of the premedicated feed and clopidol was determined in liver and muscle samples by a sensitive gas-liquid chromatography (g.l.c.) method. During the first two post-withdrawal days the clopidol concentration in the liver decreased rapidly from 7 to 0.5 mg/kg and the level in muscle declined from 3 to 0.1 mg/kg. There was little decline in the clopidol concentrations from days 2 to 10, the levels during this period being 0.2-0.8 mg/kg in liver and 0.05-0.2 mg/kg in muscle. In addition to the above experimental study, liver and muscle samples collected at a Swedish slaughterhouse from broiler chickens raised on clopidol-containing feed were analysed for residues of this drug. Large variations were found in the clopidol levels in broilers from different producers. The levels in the liver ranged from 0.05 to 8.0 mg/kg and those in muscle from 0.03 to 3.5 mg/kg. The present results emphasize the need to carry out field studies to check the levels of feed additive residues in edible tissues from chickens.