Abstract  The design and use of a rain sampler with a 0.89 m2 collection surface area were described. The sampler was controlled electronically, provided for the in situ filtration of the sample and carried out the preconcentration of nonpolar organic compounds by means of cartridges of the sorbent Tenax-GC. The possibility existed for including cartridges of ion-exchanging resin in the sampling train to provide for the preconcentration of organic acids. Analytical results were obtained for 27 compounds by fused silica capillary column gas chromatography with detection by mass spectrometry for 4 rain events sampled 12 km southwest of Portland, OR (USA), at the Oregon Graduate Center (OGC), and for 5 rain events sampled in Southeast Portland. Mean dissolved rain concentrations for alpha-BHC, naphthalene, acenaphthylene, fluorene and phenanthrene were 5.9, 11, 4.7, 3.2 and 24 ng/l, respectively, at OGC. The mean values for the Portland events were 47, 72, 55, 43 and 140 ng/l, respectively. Since dissolved concentrations were measured, the data were also used in conjunction with available Henry's law constants to estimate the concurrent, local atmospheric levels (H) of these compounds at these sites. Many of the H values of interest were available only near 298? K. The further understanding of the wet deposition of toxic organic compounds will be facilitated by the direct study of wet deposition and by the determination of the temperature dependence of the H values of environmentally interesting compounds.

Abstract  Seven acidic sulfur-containing metabolites were isolated from mouse urine following administration of naphthalene. The metabolites have been identified as (1-hydroxy-1,2-dihydro-2-naphthalenylthio)acetic acid (I), 2-hydroxy-3-(1-hydroxy-1,2-dihydro-2-naphthalenylthio)propanoic acid (II), (1,2,3-trihydroxy-1,2,3,4-tetrahydro-4-naphthalenylthio)acetic acid (III), and N-acetyl-S-(1-hydroxy-1,2-dihydro-2-naphthalenyl)-L-cysteine (IV). The dehydration products of I, II, and IV, namely 1-(naphthalenylthio)acetic acid (V), 2-hydroxy-3-(1-naphthalenylthio)propanoic acid (VI), and N-acetyl-S-(1-naphthalenyl)-L-cysteine (VII), respectively, were also present in several urinary extracts. Nine methylthio derivatives were identified in the neutral extract of urine. These metabolites were the following: 1-methylthionaphthalene, trans-1-hydroxy-2-methylthio-1,2-dihydronaphthalene, two stereoisomeric 1,2,3-trihydroxy-4-methylthio-1,2,3,4-tetrahydronaphthalenes, 1,3-di(methylthio)-2,4-dihydroxy-1,2,3,4-tetrahydronaphthalene, 1,4-di(methylthio)-2,3-dihydroxy-1,2,3,4-tetrahydronaphthalene, two methylthiohydroxy-naphthalenes, and a methylthiodihydroxydihydronaphthalene. Following intraperitoneal administration of N-acetyl-S-(1-hydroxy-1,2-dihydro-2-naphthalenyl)-L-cysteine to mice, the acidic metabolites I, II, and unchanged IV were found. The gas-chromatographic and gas chromatographic-mass spectral properties of the methyl ester-trimethylsilyl derivatives of the acidic sulfur metabolites of naphthalene are presented.

Abstract  Naphthalene is a bicyclic aromatic hydrocarbon with the chemical formula C10H8 and a molecular weight of 128.16. Pure naphthalene forms a white crystalline solid at room temperatures whereas the crude or technical grades may range in color from brown to tan. Naphthalene vapor and dust can form explosive mixtures with air. Pure naphthalene melts at 80?C; the less pure forms of the compound will melt at temperatures ranging from 74 to 80?C. The boiling point of naphthalene is 217.96?C at atmospheric pressure. At 15.5?C, the density is 1.145 and at 100?C the density is 0.9625. At 19.8?C the vapor pressure of solid naphthalene is 0.0492 mm Hg. The solubility of naphthalene in water has been reported to range between 30,000 ug/l and 40,000 ug/l at 25?C. The solubility of naphthalene in sea- water will vary according to the degree of salinity; in seawater of average composition the solubility of naphthalene is approximately 33,000 ug/l. Naphthalene has also been reported to be soluble in organic solvents. Naphthalene can oxidize in the presence of light and air, and it was determined that 50 percent of the theoretical CO2 was liberated after 14 days. However, this oxidation process occurs only at elevated temperatures. Microorganisms can degrade naphthalene to 1,2-dihydro-1,2-dihydroxy- naphthalene and ultimately to carbon dioxide and water. Studies have indicated a degradation rate under laboratory conditions of up to 3.3 ug/l. Daphnia magna is the only tested freshwater invertebrate species and the 48-hour EC50 is 8,750 ug/l. DeGraeve et al. (1980) conducted flow-through tests with measured concentrations for the rainbow trout and the fathead minnow. The trout appeared to be a little more sensitive with a 96-hour LC50 of 2,300 ug/l. The 96-hour LC50 for the fathead minnow tested at 14?C was 4,900 ug/l and at 24?C the LC50 was 8,900 ug/l. The LC50 of 150,000 ug/l for the mosquito- fish appears to be atypical but the result cannot be discounted. The results of an embryo-larval test with the fathead minnow demonstrated adverse effects at a naphthalene concentration of 850 ug/l. The resultant chronic values, 620 ug/l, provides an acute-chronic ratio of 11. Freshwater algae appear to be less sensitive with effect concentrations of about 33,000 to 34,000 ug/l. The bioconcentration factor for naphthalene and a copepod is 5,000 and this high result suggests a need for additional testing. The saltwater fish and invertebrate species tested are of about similar sensitivity to the freshwater species, with 96-hour-LC50 values of 3,800 ug/l for a polychaete and 2,350 ug/l for the grass shrimp. There was an apparently atypical 48-hour value for the Pacific oyster of 199,000 ug/l. The most critical data are those on histopathological effects on a high percentage of mummichog exposed to concentrations of naphthalene between 2 and 20 ug/l. Aquatic Life: The available data for naphthalene indicate that acute and chronic toxicity to freshwater aquatic life occur at concentrations as low as 2,300 and 620 ug/l, respectively, and would occur at lower concentrations among species that are more sensitive than those tested. The available data for naphthalene indicate that acute toxicity to saltwater aquatic life occurs at concentrations as low as 2,350 ug/l and would occur at lower concentrations among species that are more sensitive than those tested. No data are available concerning the chronic toxicity of naphthalene to sensitive saltwater aquatic life. Human Health: Using the present guidelines, a satisfactory criterion cannot be derived at this time because of the insufficiency in the available data for naphthalene.

Abstract  The development of naphthalene cataracts was studied in 5 strains of rattus norvegicus of different pigmentation. Whereas all animals of the pigmented strains (E3, BDE, DA) developed zonular cataracts after latencies of 20 to 28 days, only some of the albinos (Wistar, Sprague Dawley) exhibited less pronounced changes after longer latencies of 32 to 61 days. The possible importance of the melanin-synthetizing enzyme phenol oxidase (tyrosinase) of the iris for the formation of the cataractogenic substance 1,2-naphthodiquinone is discussed.

Abstract  BIOSIS COPYRIGHT: BIOL ABS. Results are presented on the correlation of the emissions of carbon monoxide (CO) and polynuclear aromatic hydrocarbons (PAH) from the combustion of pulverized bituminous coal and tire-derived fuel. The particle size cuts of coal and tire crumb were 63-75 and 180-212 mum, respectively. Combustion experiments were conducted in laboratory-scale facilities under controlled conditions. The relation between CO and PAH species in the combustion effluent was investigated at drop-tube furnace gas temper range) at a fixed gas temperature. The CO and especially the PAH yields from tire-derived fuel were much higher than those from coal, but the relative amounts of individual PAH components were remarkably similar in the combustion effluent of the two fuels. At fixed bulk equivalence ratios, however, as the furnace gas temperature increased the PAH yields from both fuels decreased drastically, while the CO yields increased. At the highest temperature tested herein (1300 ?C), the e

Abstract  INTRODUCTION An increased risk of lung cancer among asphalt workers has been suggested in epidemiological studies largely based on routine statistics and record linkages [Partanen and Boffetta, 1994]. Given the importance of bitumen and its fume as occupational and environmental exposures, it is important to clarify whether (i) asphalt workers are at increased risk of cancer of the lung, and possibly other organs, and (ii) whether any excess risk can be attributed to exposure to bitumen fume or other agents, such as coal tar. The International Agency for Research on Cancer (IARC) and its collaborators assembled a retrospective cohort of asphalt workers from the asphalt industry (road paving, asphalt mixing, and roofing) in seven European countries (Denmark, Finland, France, Germany, the Netherlands, Norway, and Sweden) and Israel. The primary goal of the study was to assess whether an increased risk of lung cancer is associated with bitumen fume exposure. Details on the study design and the detailed results of the mortality analysis have been reported [Boffetta et al., 2001]. In a companion paper, we report the results of the analysis of mortality based on employment in specific job groups [Boffetta et al., 2003]. In this article, we report results based on assessment of exposure to bitumen and other agents.

Abstract  BIOSIS COPYRIGHT: BIOL ABS. Available data for three New York City landfills constructed prior to 1925 are compiled to evaluate the presence and characteristics of seven non-alkylated polycyclic aromatic hydrocarbon (PAH) compounds in solid waste and pore waters. PAH compounds were detected in 90% of 154 waste samples. The median and maximum total PAH concentrations in waste were 7,010 and 277,200 ug/kg, respectively. A characteristic pattern in the relative abundance of seven PAH compounds is observed for most waste samples. Peak abundances are seen for PAH compounds in the middle molecular weight range (mw = 178-226). Progressively lower concentrations are observed for PAH compounds that are heavier or lighter than this range. Three compounds, phenanthrene, pyrene and chrysene, typically account for more than 35% of the total PAH in waste. The total PAH concentration is highly variable with depth and location and is probably dependent on random local variability of waste. Differences in the aque

Abstract  National Heart, Lung, and Blood Institute; U.S. Environmental Protection Agency; U.S. Department of Energy.

Abstract  HEEP COPYRIGHT: BIOL ABS. A systematic effort was made to identify components in the neutral polar fraction of carbon black extract as well as the constituents of the polycyclic aromatic hydrocarbon fraction. One aromatic hydrocarbon in environmental samples whose structure has not been elucidated is cyclopenta(cd)pyrene. The method employed to deduce its structure should be of general utility for polycyclic aromatic hydrocarbons. UV, IR, and mass spectrometry were used to identify compound 10 as phenalenone. Although the neutral polar fraction of airborne particulate matter, which might be closely related in composition to the neutral polar fraction of carbon black, has been shown in possess considerable carcinogenic potency, concerted efforts have not been made to identify the polar compounds either in airborne particulates or carbon black. Screening the neutral polar compounds identified in carbon black for carcinogenic activity might be useful in discovering hitherto unsuspected environmental carcinogens.

Abstract  Italian Ministry of Environment. #The effect of fuel composition on the mutagenicity of diesel engine emission was investigated. To this end, a fuel matrix comprising fuels with different contents of aromatic and naphthenic compounds was used. Extracts of the organic phase of raw exhausts obtained with different fuels were tested for mutagenicity in bacterial reversion assays. The results obtained demonstrate that the mutagenicity of diesel exhaust is largely dependent on the aromatic content of the fuel. In fact, mutagenicity was greatly reduced when the aromatic content of the fuel was lowered by hydrogen treatment. Conversely, mutagenicity was enhanced when the fuel was enriched with fractions of di- or triaromatic compounds. The addition of di- and trinaphthenic compounds only produced borderline mutagenicity. No clear relationship was observed between sulfur content of the fuel and mutagenicity of the exhaust. Assays in bacterial strains with different sensitivity to nitroaromatic compounds suggest a low contribution of the highly mutagenic dinitropyrenes to the responses observed, and a relatively greater contribution of 1-nitropyrene or other nitroaromatics processed by the same bacterial nitroreductase.

Abstract  Air samples from a rural forested site in the Sierra Nevada Mountains were analyzed for volatile organic compounds by a thermodesorption GC/MS technique. Approximately 120 compounds were characterized by their mass spectra, with identification achieved for about 70 of these substances. A high proportion of biogenically emitted substances was found and the concentration of anthropogenic chemicals was relatively low. Twenty-one terpenoid compounds (C10H16 and oxygenated derivatives) and p-cymene were identified, and a single sesquiterpene, tentatively identified as longifolene, was also found. Nopinone (bicyclo[3.1.1]-heptan-2-one, 6,6-dimethyl-) and alpha-pinene oxide (3-oxatricyclo-[4.1.1.02,4]-octane, 2,7,7-trimethyl), both possible pinene degradation products, were among the compounds detected, although it is possible that the observed levels of one or both of these included contributions from formation during the sampling. The strong influence of local vegetative emissions on the composition of the forest air was confirmed by quantitative analysis. Concentrations of single monoterpenes up to 6.8 micrograms m-3 were found, whereas toluene was in the range of 0.3 micrograms m-3. The results from the forest site are compared with urban air samples collected in Riverside, California.

Abstract  Neurotoxicity has been described in workers exposed to solvents, PCBs, certain metals, and polyaromatic hydrocarbons but not often in residents near refineries or factories. We compared the neurobehavioral performance of residents near a plant that reprocessed used motor oil and chemical waste from 1966?1983 to referents from beyond the plant's modeled air dispersal and water drainage zones. Neurophysiological and psychological tests, a Profile of Mood States (POMS) and a symptom questionnaire were administered to 131 subjects exposed at the site who were matched for age, sex, and ethnicity 2:1 with 66 unexposed subjects from 35 km away. Test scores were adjusted for a 1.4-year difference in educational attainment by coefficients from regression equations but not for income as the latter coefficients were not significant. Exposed subjects were significantly impaired for body balance (sway speed) and simple and two choice visual reaction time as compared to referents. Blink reflex latency (R-1) and eye closure speed were normal in both groups. Cognitive function in the exposed was impaired as measured by Culture Fair and by block design from the WAIS. Placing pegs in a grooved board and making of trails (A and B) were also impaired. Group differences in recall and memory were not significant. The exposed group's symptom frequencies and POMS scores for depression, anger, confusion, tension, and fatigue were elevated indicating depression. Confounding from medical and neurological disorders or occupational exposures was minimal. Subjects exposed residentially for up to 17 years to chemicals dispersed from a waste oil reprocessing plant showed neurophysiological and neuropsychological impairment.

Abstract  A sensitive and rapid method for the determination of lanthanum, europium and ytterbium by inductively coupled plasma atomic emission spectrometry (ICP-AES) after solid-liquid extraction with microcrystalline naphthalene was developed. Analytes could be quantitatively adsorbed on tribromoarsenazo-cetylpyridinium bromide-naphthalene (TBA-CPB-naphthalene) packed in a column and determined by ICP-AES after desorption with 3 moll(-1) HCl. The effect of various experimental parameters, such as pH, reagent amounts, naphthalene concentrations and diverse ions, on the determination of interesting elements were investigated in detail. Under the optimized experimental conditions, the detection limits of this method for La(3+), Eu(3+) and Yb(3+) were 1.3-8.6 ngml(-1), and the relative standard deviations obtained for nine replicate determinations at a concentration of 0.5 mugml(-1) were 1.4-2.2%. The proposed method has been applied in the analysis of NIES CRM No. 8 vehicle exhaust particulates and GBW 07602 GSV-1 bush branches and leaves for La, Eu and Yb, and La in NIST SRM 1752 citrus leaves samples; the analytical results were in good agreement with reference values.

Abstract  In an effort to lessen the environmental impact of chemicals discharged by industry, some countries rank chemicals according to mass released each year and then set environmental protection policy based upon this ranking. These rankings have driven industries and companies to change their process configurations and their chemical releases to reduce the release of higher ranking chemicals. But, chemicals that are higher ranked due to mass release may not be particularly toxic nor persistent in the environment; conversely, lower ranked chemicals may be substantially more toxic and persistent in the environment. The physical/chemical properties of forty five organic chemicals from the EPA's Toxic Release Inventory were used as inputs to a Level III fugacity model to estimate fate, transport, and steady state concentrations of chemicals in the environment. The resulting concentrations in the air and water, for each chemical, were determined using the fugacity model and were then compared with toxicity data, the ratio was used as an indication of the environmental impact of the release of each chemical. The chemicals were then ranked according to the degree of environmental impact and the results were compared to other ranking systems reported in the literature.

Abstract  The objective of this study was to characterize volatile organic compounds (VOCs) found at municipal structural fires in order to identify sources of long-term health risks to firefighters, which may be contributing factors in heart disease and cancer. Firefighters collected air into evacuated Summa canisters inside burning buildings at nine municipal structural fires under conditions where they judged that at least some firefighters might remove their self-contained breathing apparatus masks. Volatile organic compounds were identified and quantified for 144 target compounds using cryogenic preconcentration and gas chromatography/mass spectral detection (GC/MSD) methodology operating in selected ion monitoring mode. Samples were also analyzed in SCAN mode and examined for the appearance of substances that were not present in the instrument standard calibration mixture. The spectra of municipal structural fires were surprisingly similar and remarkable for their simplicity, which was largely due to the dominating presence of benzene along with toluene and naphthalene. Propene and 1,3-butadiene were found in all of the fires, and styrene and other alkyl-substituted benzene compounds were frequently identified. Similar "fingerprints" of the same 14 substances (propene, benzene, xylenes, 1-butene/2-methylpropene, toluene, propane, 1,2-butadiene, 2-methylbutane, ethylbenzene, naphthalene, styrene, cyclopentene, 1-methylcyclopentene, isopropylbenzene) previously identified at experimental fires burning various solid combustible materials were also found at municipal structural fires, accounting for 76.8% of the total VOCs measured. Statistically significant positive correlations were found between increasing levels of benzene and levels of propene, the xylenes, toluene, 1-butene/2-methylpropene, 1,3-butadiene, and naphthalene. Given the toxicity/carcinogenicity of those VOCs that were found in the highest concentrations, particularly benzene, 1,3-butadiene, and styrene, further investigation of VOC exposures of firefighters is warranted. Benzene, or its metabolic product s-phenylmercapturic acid in urine, was identified as a suitable chemical marker for firefighter exposure to combustion products

Abstract  The performance of six different bioluminescent bacteria for the assessment of oil bioremediation was compared. Three contained lux genes linked to promoters from hydrocarbon degradation pathways: Pseudomonas fluorescens HK44 (pUTK21), Escherichia coli HMS174 (pOS25) and E. coli DH5 alpha (pGEc74, pJAMA7), responding to naphthalene, isopropylbenzene and octane, respectively. The other three expressed lux constitutively: E. coli HB101 (pUCD607) and P. putida F1 (pUCD607) are genetically engineered, while Vibrio fischeri is naturally bioluminescent and was included to facilitate comparison with previous work. Five different oils (four crude oils plus diesel) were spiked into soil, and the progress of remediation was followed over a period of 119 d by monitoring both hydrocarbon disappearance and changes in the microbial response to soil extracts. The octane bioassay was the only one of the hydrocarbon-responsive bacterial assays to show any appreciable response, with up to 20-fold induction by light crude oils. Heavy crude oil and diesel elicited a much weaker response. The metabolic (lux constitutively expressed) bioassays showed that there was a general increase in toxicity over the course of the experiment, although toxicity to E. coli HB101 (pUCD607) appeared to be decreasing by the final sampling point. The metabolic bioassay response was much less variable between the different oils than for the first three, catabolic, strains.

Abstract  A miniature ion trap mass analyzer was applied to the analysis of traces of hydrocarbons and simple heteroatomics in the vapor phase and in aqueous solution. Vapors of acetone, acetic acid, acetonitrile, benzene, butanethiol, carbon disulfide, hexane, dichloromethane, naphthalene, toluene and xylenes were detected and quantified using solid sorbent trapping and, in some cases, by passage through a membrane interface. Aqueous solutions of benzene, toluene, xylenes, hexane and a petroleum naphtha distillate were examined using the membrane interface. Sampling, detection and identification of all compounds was completed in times of less than one minute. The gas-phase samples of toluene and benzene were detected at 200 ppt (limit of detection, LOD) for toluene and 600 ppt for benzene. Identification of benzene and xylene in aqueous solutions was readily achieved with LODs of 200 and 400 ppb, respectively. Quantification over a linear dynamic range of two orders of magnitude for the aqueous samples and three orders of magnitude for the vapor-phase samples was demonstrated.

Abstract  Final Technical rept. 1 Apr 96-31 Dec 98. Funded studies focused on the biodegradation of three nitroaromatic compounds, nitrobenzene, 2-nitrotoluene, and 2,4-dinitrotoluene, by bacterial strains isolated in Dr. Jim C. Spain's laboratory, Tyndall AFB. Genes and enzymes required for the degradation of these compounds were characterized. Several genes involved in the degradation of nitrobenzene and phenol from Comamonas sp. strain JS765 were cloned and sequenced. A gene cluster from Pseudomonas sp. strain JS42 encoding 2-nitrotoluene dioxygenase was cloned and sequenced and was found to be related to gene clusters from Burkholderia sp. strain DNT and Pseudomonas sp. strain NOIB 9816-4 which encode 2,4- dinitrotoluene and naphthalene dioxygenases, respectively. The ntd gene cluster cloned in E. coil proved useful in studies that demonstrated that the C-terminal half of the alpha subunit of the oxygenase component of 2-nitrotoluene dioxygenase is responsible for determining the substrate specificity of the enzyme. Construction and analysis of hybrid dioxygenases demonstrated that the oxygenase beta subunits of naphthalene, 2-nitrotoluene and 2,4-dinitrotoluene dioxygenases do not play a role in determining substrate specificity.

Abstract  In order to determine the sources of pollution of surface waters, an investigation into the occurrence of black list substances in two river basins has been made. Both rivers, “Voorste Stroom” and “Mark-Dintel”, are transboundary ones, coming from Belgium, and both rivers of discharge indirectly into the North Sea. The “Voorste Stroom” flows through a rural area with a number of natural parks. The area of the “Mark-Dintel” is more industrialized and the downstream polders are in agricultural use. Over 75,000 samples have been taken throughout a whole year, and have been analyzed on the presence of over one hundred substances, a large number of them belonging to the black list of the European Community. Not only the surface waters and sediments of the “Voorste Stroom” and the “Mark-Dintel” have been sampled in various places but also the surface waters of upstream rivers, flowing to these two basins. The effluents of all the municipal wastewater treatment plants in the area have been analyzed. Furthermore, a number of industries discharging into these sewage systems, were taken into account. In the whole area of the two basins, 82 out of 121 substances have been found to be present once or more in the surface water, leaving 39 that have not been found at all. Only 14 substances were frequently present, i.e. in over 50% of all the surface water samples. Another 17 substances were present in frequencies between 30 and 50%. The substances withe the highest frequencies belong predominantly tot the polycyclic aromatic hydrocarbons (PAH) and to the polychlorobiphenyls (PCB). In spite of the large number of samples it was not possible to trace the real sources of all the substances polluting the surface water of the “Voorste Stroom” and “Mark-Dintel”. In a small number of cases the discharge from a municipal waste water treatment plant was of major importance tot the surface water quality, but within this study it was not possible to trace the discharge into the sewerage system. In all other cases the pollution seems to be from diffuse sources: groundwater, agricultural run-off, transboundary transport, and urban run-off. Nevertheless, more insight into the importance of the loads from the upstream rivers has been gained. The relative importance of the loads within these two areas to the North Sea may be calculated.

Abstract  Biosis copyright: biol abs. rrm resource conservation and recovery act