Fluoranthene, atmosphere

Lane, D.A., Katz, M. (1977) The photomodification of benzo(a)pyrene, benzo(i> (fluoranthene, and benzo(k)fluoranthene under simulated atmospheric conditions. Adv. Environ. Sci. Technol. 8, 137-154. 

Fig. 5a-c. A typical distribution of polycyclic aromatic hydrocarbons in a atmospheric fallout sample, Alexandria City - Egypt b bottom incineration ash leachate of municipal solid waste - USA c hydrothermal petroleum, Escanaba Trough, NE Pacific Ocean. PAH Compound identifications N = naphthalene, MN = methylnaphthalene, DMN = dimethylnaphthalenes, P = phenanthrene, MP = methylphenanthrene, Fl = fluoranthene, Py = pyrene, BaAN = benzol anthracene, DH-Py = dihydropyrene, 2,3-BF = 2,3-benzofluorene, BFL = benzo[fc,/c]fluoranthene, BeP = benzo[e]pyrene, BaP = benzo[a]pyrene, Per = perylene, Cx-228 = methyl-228 series, Indeno = indeno[ l,2,3-c,d]pyrene, DBAN = dibenz[a,/z]anthracene, BPer = benzo[g,/z,z] perylene, AAN = anthanthrene, DBTH = dibenzothiophene, Cor = coronene, DBP = dibenzo [a,e]pyrene, DBPer = dibenzo [g,h,i] perylene... 

Photolytic. The atmospheric half-life was estimated to range from 1.1 to 11 h (Atkinson, 1987). Chemical/Physical. Benzo[i]fluoranthene will not hydrolyze because it has no hydrolyzable... 

Chemical/Physical. 2-Nitrofluoranthene was the principal product formed from the gas-phase reaction of fluoranthene with OH radicals in a NOx atmosphere. Minor products found include 7-... 

Finally, while several volatile and semivolatile PAHs, e.g., naphthalene, the methylnaphthalenes, phenan-threne, pyrene, and fluoranthene, are not significant mutagens or carcinogens (hence not included in Table 10.13), they are precursors to powerful direct bacterial mutagens formed in gas-phase atmospheric reactions with hydroxyl during the day and nitrate radicals at night (see Section F). Furthermore, 2-nitrofluoranthene,... 

BaP, benzo[g/z/]perylene, benzo[6]fluoranthene, in-deno[l,2,3-cd]pyrene, and benzo[/c]fluoranthene, contribute the major portion of the identifiable mutagenicity of the extract of the whole unfractionated sample, accounting for 8.6, 2.5, 1.7, 1.4, 1.2, and 0.8%, respectively, of the total mutagenicity of the whole sample. Two semipolar mutagenic PACs were also present at significant levels 2-nitrofluoranthene, a product of atmospheric reactions, and 6//-benzo[c<7]pyren-6-one, a primary O-PAC pollutant present in exhaust emissions from diesel engines and non-catalyst-equipped cars (see Sections E and F). These account for an additional 0.8 and 1.6%, respectively, of the identified whole sample mutagenic potency (see Table 10.26). 

Lane and Katz reported in 1977 that the dark reaction of BaP deposited on the surface of glass Petri dishes with air containing 200 ppb of ozone was fast, with a half-life of —38 min. Katz and co-workers (1979) exposed nine PAHs on thin-layer chromatography plates of cellulose in the dark to 200 ppb of O, in air and found pronounced differences in their reactivities, e.g., half-lives of 36 min for BaP, 2.9 h for BaA, 7.6 h for BeP, and 53 h for benzol b ]fluoranthene. Subsequently, in good agreement with Lane and Katz, a half-life of -1 h was determined for BaP deposited on glass fiber filters and exposed (passively in a controlled atmosphere) to 200 ppb of 03 in the dark (Pitts et al., 1980). 

Attack by OH radicals on the gas-phase fluoranthene and pyrene must be fast. As seen in Table 10.35, again this is true. In Table 10.36, the calculated atmospheric lifetimes of selected gas-phase PAHs due to reaction with OH are shown, e.g., lifetimes of 2.9 h for fluoranthene and pyrene. 

Figure 10.35 is the GC-MS m/z 247 profile of the nitrofluoranthenes and nitropyrenes in an extract of an ambient particle sample collected at night (Arey et al., 1988b). The high ratio of 2-nitrofluoranthene to 2-nit-ropyrene observed in this nighttime sample is indicative of nighttime gas-phase NO, radical reactions (for a review, see Kwok et al., 1994b). An NO, radical initiated mechanism for atmospheric formation of 2-nitrofluoranthene is shown in Fig. 10.36 (Atkinson and Arey, 1997 Arey, 1998a, and references therein). Analogous to the OH reaction, NO, is proposed to add to the ring to form a fluoranthene-NO, adduct, followed by ortho addition of N02 and subsequent loss of HNO,. This reaction is noteworthy because of its selectivity i.e., only 2-nitrofluoranthene is formed, and in high yield (24%) compared to the OH-initiated daytime reaction (3%).

Figure 1. Gas chromatogram of PAH in a work atmosphere a, particulate PAH b, gaseous PAH. The peak identities are 1, naphthalene 2, 2-methylnaphthalene 3, 1 -methylnaphthalene 4, biphenyl 5, acenaphthene 6, dibenzofuran 7, fluorene 8, 2-methylfluorene 9, 1-methylfluorene 10, dibenzothiophene 11, phenanthrene 12, anthracene 13, methylphenanthrene/methylanthracene 14, methylphenan-threne/methylanthracene 15, 2-methylanthracene 16, 4,5-methylenephenanthrene 17, methylphenanthrene/methylanthracene 18,1-methylphenanthrene 19, fluoranthene 20, benzo(def)dibenzothiophene 21, pyrene 22, ethylmethylenephena-threne 23, benzo(a)fluorene 24, benzofb)fluorene 25, 4-methylpyrene 26, meth-ylpyrene 27, 1-methylpyrene 28, benzothionaphthene 29, benzo(c)phenanthrene 30, benzophenanthridine 31, benzo(2i)anthracene 32, chrysene/triphenylene 33, benzo(b)fluoranthene 34, benzof])fluoranthene 35, benzo(k)fluoranthene 36, ben-zo(c)pyrene 37, benzofa)pyrene 38, perylene 39, indenof 1,2,3-cd)pyrene 40, dibenz(a, /a,h)anthracenes 41, benzofghi)perylene 42, anthanthrene 43, coro-...

The kinetic/thermodynamic isomer ratios of phenanthrene anthracene (three-ring) and pyrene fluoranthene (four-ring) were derived from PAH marine sediment data for Singapore, and are shown in Fig. 15.11. An abundance of high molecular weight PAHs is typical of atmospheric... 

Figure 2 shows fluorescence spectra for pyrene and fluoranthene in atmospheric pressure cells pumped at essentially the same wavelength. These spectra are typical of the types of profiles obtained for PCAH. The spectra are broad band with no significant fine structure. Comparison of the two spectra... 

Figure 2. Fluorescence spectra—atmospheric pressure cell (air) upper figure, pyrene at 78°C . lower figure, fluoranthene at 90°C fluorescence-analyzing bandpass of 4 run.

Humoral immunity was monitored in male iron foundry workers in Poland (Szczeklik et al. 1994). Coke oven workers (199) were compared to cold-rolling mill workers (76). The groups were similar with respect to age, length of employment, and smoking habits. The results showed that coke oven workers, exposed to high concentrations of atmospheric PAHs, including fluoranthene, perylene, pyrene, benzo[a]pyrene, chrysene, benz[a]anthracene, dibenz[a,h]anthracene, and... 

Several studies have been carried out to investigate the reaction of PAHs with ozone at ambient concentrations (Baek et al. 1991). Alebic-Juretic et al. (1990) found degradation of PAHs on particle surfaces by ozone to be an important pathway for their removal from the atmosphere. Half-lives of PAHs obtained under laboratory conditions were used to predict lifetimes in an atmosphere containing a constant ozone concentration of 0.05 ppm. The predicted lifetimes were 3 hours for benzo[a]pyrene, 12 hours for pyrene, and 6 days for fluoranthene. Lane and Katz (1977) investigated the kinetics of the dark reaction of several PAHs with ozone and found the reaction to be extremely fast under simulated atmospheric conditions, with a reported half-life of 0.62 hours for benzo[a]pyrene exposed to 190 ppb of ozone. 

Several other studies provide evidence that atmospheric concentrations of particle-phase PAHs are higher in winter than in summer. In a 1981-82 study conducted in the Los Angeles area, atmospheric concentrations of 10 PAHs (anthracene, fluoranthene, pyrene, chrysene. benz[a]anthracene. combined benzo[a]pyrene and perylene, benzo[b]fluoranthene. benzo[k]fluoranthene. 

Fox and Staley (1976), which ranged from 66 ng/m for benzo[a]pyrene to 120 ng/m for pyrene. Benner and Gordon (1989) postulated that the observed decrease in PAH concentrations over the 1975-85 decade resulted from the increasing use of catalytic converters in U.S. automobiles over that period. These authors also reported concentrations of PAHs in a typical vapor-phase sample from the Boston Harbor Tunnel for four PAHs included in this profile anthracene (32.3 ng/m ), fluoranthene (25.6 ng/m ), phenanthrene (184 ng/m ), and pyrene (28.3 ng/m. They emphasized that the vapor-phase samples included PAHs inherently present in the vapor phase as well as the more volatile 3- and 4-ring PAHs that may be desorbed from particles during sampling. These results underscore the need to evaluate both particle- and vapor-phase samples to obtain more reliable estimates of total atmospheric PAH concentrations. 

Figure 7.13 Results obtained for the atmospheric microwave-assisted extraction of various polycyclic aromatic hydrocarbons from contaminated soil, and comparison with those obtained from Soxhlet extraction , Soxhlet , aMAE 1, naphthalene 2, acenaphthylene 3, acenaphthene 4, fluorene 5, phenanthene 6, anthracene 7, fluoranthene 8, pyrene 9, benz[a]anthracene 10, chrysene 11, benzo[fr, ]fluoranthene 12, benzo[a]pyrene 13, indeno[l,2,3-cd]pyrene 14, benzo[gfe ]pyrene [1] (cf. DQ 7.10).

On a hot, sunny day evaporation of creosote from the surface of treated wood may release coal tar creosote constituents to the atmosphere. Only the volatile creosote components such as acenaphthene and naphthalene will volatilize the heavier fractions will remain on the wood (E1SDA 1980). Volatilization may also be greater during warmer months when ambient temperatures are higher. Gevao and Jones (1998) observed greater volatilization of acenaphthene, fluorene, phenanthrene, anthracene, and fluoranthene from creosote-treated wood at 30 °C than at 4 °C. 

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