Chrysene, detection

Figure 12.21 SFC-GC heait-cut analysis of chrysene from a complex hydrocarbon mixture (a) SFC ttace (UV detection) (b) GC trace without heait-cut (100% transfer) (c) GC ti ace of heatt-cut fraction (flame-ionization detection used for GC experiments). Reprinted from Journal of High Resolution Chromatography, 10, J. M. Levy et al., On-line multidimensional supercritical fluid chromatography/capillaiy gas cluomatography , pp. 337-341, 1987, with permission from Wiley-VCFI.

Figure 3 depicts profiles of Total PAH fluxes vs. time (36). The following polycyclic hydrocarbons have been determined by high performance liquid chromatography, variable wavelength absorption detection Naphthalene, acenaphthylene, 7,12-dimethylbenzanthracene, 2-methylnaphtalene, fluorene, acenaphtene, phenanthrene, 2,3-dimethylnaphtalene, anthracene, fluoranthene, 1-methylphenanthrene, pyrene, 2,3-benzofluorene, triphenylene, benz(a)anthracene, chrysene, benzo(b)fluoranthene, benzo(k)fluoranthene, perylene, benzo(e)pyrene, 1,2,3,4-dibenzanthracene, benzo(a)pyrene, and 1,2,5,6-dibenzanthracene. 

The most significant differences (i.e. independence) in the analytical methods are provided in the final chromatographic separation and detection step using GC/ MS and LC-FL. GC and reversed-phase LG provide significantly different separation mechanisms for PAHs and thus provide the independence required in the separation. The use of mass spectrometry (MS) for the GC detection and fluorescence spectroscopy for the LG detection provide further independence in the methods, e.g. MS can not differentiate among PAH isomers whereas fluorescence spectroscopy often can. For the GC/MS analyses the 5% phenyl methylpolysiloxane phase has been a commonly used phase for the separation of PAHs however, several important PAH isomers are not completely resolved on this phase, i.e. chrysene and triphenylene, benzo[b]fluoranthene and benzofjjfluoranthene, and diben-z[o,h]anthracene and dibenz[a,c]anthracene. To achieve separation of these isomers, GC/MS analyses were also performed using two other phases with different selectivity, a 50% phenyl methylpolysiloxane phase and a smectic liquid crystalline phase. 

Organic compounds polycyclic aromatic hydrocarbons, in particular phenan-threne (C14H10), pyrene (Ci6Hjo) and chrysene (CisH ), which were detected using high resolution mass spectrometry. 

Nitro polycyclic aromatic hydrocarbons are environmental contaminants which have been detected in airborne particulates, coal fly ash, diesel emission and carbon black photocopier toners. These compounds are metabolized Tn vitro to genotoxic agents through ring oxidation and/or nitroreduction. The details of these metabolic pathways are considered using 4-nitrobiphenyl, 1- and 2-nitronaphthalene, 5-nitro-acenaphthene, 7-nitrobenz[a]anthracene, 6-nitro-chrysene, 1-nitropyrene, 1,3-, 1,6- and 1,8-dinitro-pyrene, and 1-, 3- and 6-nitrobenzo[a] pyrene as examples ... 

Finally, three additional individual data matrices were obtained for soil (so1 so2, and so3), in this case with the same number of samples (rows) for each of them. A new soil data matrix (SO) was obtained after individual matrix concatenation containing 36 samples in total (12 samples analyzed in 3 sampling campaigns) (see Fig. 7). Fifteen variables (all of them detected in SE as well) were measured in every sample PAHs (acenaphtylene, phenanthrene, anthracene, fluoranthene, pyrene, benzo(a)anthracene, chrysene, benzo(b)fluoranthene, benzo(a)pyrene, indeno (l,2,3-cd)pyrene, dibenzo(a,h)anthracene, and benzo(g,h,i)perylene), an organophosphate compound (tributylphosphate), and an OC (4,4 -DDE). 

A gas chromatography-flame ionization detector system can be nsed for the separation and detection of nonpolar organic componnds. Semivolatile constitnents are among the analytes that can readily be resolved and detected nsing the system. If a packed column is used, four pairs of compounds may not be resolved adequately and are reported as a quantitative sum anthracene and phenanthrene, chrysene and benzo[a]anthracene, benzo[/ ]fluoranthene and benzo[/ ]fluoranthene, and dibenzo[a,/i]anthracene and indeno[l,2,3-cd]pyrene. This issue can be resolved through the use of a capillary column in place of a packed column. 

Detected in groundwater beneath a former coal gasification plant in Seattle, WA at a concentration of 10 pg/L (ASTR, 1995). The concentration of chrysene in coal tar and the maximum concentration reported in groundwater at a mid-Atlantic coal tar site were 3,600 and... 

Chrysene was detected in asphalt fumes at an average concentration of 115.67 ng/m (Wang et ah, 2001). 

The surrogate compounds were mono-, tetra-, octa-, deca- C-PCBs, dg-naphthalene, C-PCP and C-phenol. The soil samples were dried with Na2S04 (60 g) and then Soxhlet extracted with hexane acetone (9 1) for 16 h. The extract was dried with sodium sulfate, concentrated, and split. While one portion was held for other analyses, the other portion was placed on a 3% deactivated silica gel column and eluted with increasing solvent polarity systems [hexane, followed by methylene chloride hexane (1 1), and then methylene chloride acetone (95 5)]. The extracts were combined and reduced to 1 mL, split and two internal standards added (tetrafluorobiphenyl and di2 Chrysene). The extracts were chromatographed on a 15-m DB-5 fused silica capillary column and detected with flame ionization (FID). Sludge samples were extracted according to the EPA sludge protocol (2) developed at Midwest Research Institute. 

FIGURE1.15 Separation of the 16 EPA priority pollutants PAHs with ODS column using an acetonitrile water 70 30 (v/v) solution as mobile phase. Thiourea was used as standard. Detection performed at 254 nm and 30°C. PAHs 1, naphthalene 2, acenaphtylene 3, fluorene 4, acenaphthene 5, phenanthrene 6, anthracene 7, fluoranthene 8, pyrene 9, chrysene 10, benz(a)anthracene 11, benzo(fc)fluoranthene 12, benzo(l )fluoranthene 13, benzo(a)pyrene 14, dibenz(a,/i)anthracene 15, indeno(l,2,3-cd)pyrene and 16, benzo(g,/j,/)perylene). (Reprinted from Nunez, O. et al., J. Chromatogr. A, 1175, 7, 2007. Copyright 2007, with permission from Elsevier.)... 

GC-MS examination of the PAH fraction of sample S2 (S2-C2) gave very similar results the total ion chromatogram is shown in Figure 5. Major constituents were phenanthrene, fluoranthene, pyrene, and methyl, dimethyl/ethylphenanthrene/anthracene. Relative abundance of some C2-alkylphenanthrenes/anthracenes were higher in this sample than in S1-C2. Smaller quantities of benzo[ghi]fluoranthene, chrysene, benzo[ajanthracene, tripheny-lene, benzo[b,j, k]fluoranthenes, and benzo[e aJpyrenes and were characterized by MS. In addition, most compounds listed in Table 1 were also detected in this sample. 

The formation of acyl-chrysenes 270 from 1-methyl-substituted ben-zo[c]pyrylium salts 266 occurs not only on heating in alkaline solutions, but also in acidic nucleophilic media (cf. Section III,C,4,b,i). However, in the latter case, together with acylchrysenes 270, their deacylated analogs 273 are formed (85KGS910). Under these conditions, the same results were obtained for conversions of diketones 29, therefore it is difficult to conclude which compound (anhydrobase 267 or diketone 29) is the intermediate in the formation of chrysenes 270 and 273 from salts 266 in acidic nucleophilic medium. It was not possible to trap or detect the dimeric pseudobase 269 under these conditions. However, the latter compound, under the described conditions or on heating in acetic acid, forms the mixture of the same products (270 and 273). 

Fig. 2.20. Composition (mean%) of 16 individual polycyclic aromatic hydrocarbons (PAHs) to total PAHs detected in various environmental media in (a) air (n = 24), (b) soil (n = 226), (c) freshwater (n = 46), and (d) marine sediment (n = 159), from the South Korea. Naphthalene NAP, Acenaphthylene ACY, Acenaphthene ACE, Fluorine FLU, Phenanthrene PHE, Anthracene ANT, Fluoranthene FLT, Pyrene PYR, Benz[a]ant-hracene BaA, Chrysene CHR, Benzo[6]fluoranthene BbF, Benzo[ ]fluoranthene BkF, Benzo[a]pyrene BaP, Indeno[l,2,3,c,d]pyrene I123cdP, Dibenz[a,/z]anthracene DahA, Ben-zo[g,/y ]perylene BghiP.

Das and Thomas [200] used fluorescence detection in high performance liquid chromatography to determine nine PAHs in occupational health samples including process waters. The nine compounds studied were benzo(a)anthracene, benzo(k)fhioranthene, benzo(a)pyrene/fhioranthene, chrysene, benzo(k)fluorene, perylene, benzo(e)pyrene, deibenz(ah)-anthracene and benz(ghi)perylene. 

Figure 17 ChEC separation of 13 PAHs (1) naphthalene, (2) acenaphthylene, (3) acenaphthene, (4) fluorene, (5) phenanthrene, (6) anthracene, (7) fluoranthene, (8) pyrene, (9) benz[a]anthracene, (10) chrysene, (11) benz[6]fluoranthene, (12) benzo[/r]fluoranthene, (13) benzo[a]pyrene Length to detection 7 cm. Max voltage 2 kV. Running buffer was 80/20 (%, v/v) acetonitrileaqueous (20 mmol/L Tris pH 8.5) Injection 2 kV, 5 min. (Reprinted from Ref. 81, with permission.)...

The distribution of the emitted PAH between the four traps, the cyclones, the condenser, the Teflon filter and the XAD-2 resin, with sand and limestone beds, is shown in Table 3. In spite that the 16 PAH listed by USEPA were comprised in this study, only Fluorene, Pyrene, Acenaphthene, Benzo(a)Anthracene and Coronene could be quantified. Three other PAH, Benzo(a)Pyrene, Chrysene and Anthracene, were detected but were emitted below quantification limits. The remaining studied PAH were not detected. 

Fractions from the LC of Synthoil and shale oil were examined also by MI FTIR spectrometry spectra of Fractions IV and V from the LC of Synthoil are shown in Figures 8 and 9, respectively. Pyrene (v = 750, 746 cm ) and chrysene v = 766, 764, 817, 814 cm" ) can be identified as present in Fractions IV and V, respectively. The other absorption bands in the FTIR spectra of Fractions IV and V cannot be assigned to the PAH for which MI spectra are available. No absorptions assignable to PAH are detected in the MI FTIR spectra of Fraction VI of Synthoil. The presence of strong absorption bands in the 2920-3000 cm" in the IR spectra of the oil fractions is indicative of the presence of alkyl groups, and it is therefore likely that the high concentrations of paraffin hydrocarbons largely obscure the IR features of PAH (presumably present in much smaller quantities). Thus, a pretreatment step (25) prior to the LC of the oil samples, to remove aliphatics, appears essential in the examination of these samples of PAH by FTIR spectrometry. 

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