Society of Petroleum Engineers

SPE 25990

Rapid Characterization of PAH's in Oils and Soils by TotalScanning FluorescenceN.R. Gray and S.J. McMillen, Exxon Production Research Co.; A.G. Requejo, Geochemical &Environmental Research Group; J.M. Kerr, Exxon Production Research Co.; and Guy Denouxand T.J. McDonald, Geochemical & Environmental Research Group

Copyright 1993, Society of Petroleum Engineers, Inc.

This paper was prepared for presentation at the SPEJEPA Exploration & Production Environmental Conference held in San Antonio, Texas, U.S.A., 7-10 March 1993.

This paper was selected for presentation by an SPE Program Committee following review of information contained in an abstract submitted by the author(s). Contents of the paper,as presented, have not been reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material, as presented, does not necessarily reflectany position of the Society of Petroleum Engineers, its officers, or members. Papers presented at SPE meetings are SUbject to pUblication review by Editorial Committees of the Societyof Petroleum Engineers. Permission to copy is restricted to an abstract of not more than 300 words. Illustrations may not be copied. The abstract should contain conspicuous acknowledg-ment of where and bY whom the paper Is presented. Write Librarian, SPE, P.O. Box 833836, Richardson, TX 75083-3836, U.S.A. Telex, 163245 SPEUT.

ABSTRACT

Total Scanning Fluorescence (TSF) is a rapid andinexpensive technique that can be used for the analysisof polynuclear aromatic hydrocarbons (PAH's). Thebasis for the use of fluorescence is that, in general,emission/excitation wavelength maxima increase withincreasing number of aromatic rings. The output of theTSF analysis is a fluorescence "fingerprint" consisting ofa 3-D emission/excitation intensity contour diagram.This "fingerprint" can provide information about thecontent and relative composition of PAH's in samples.

To date, this technique has been applied primarily to theanalysis of sediment samples collected as part ofoffshore geochemical exploration programs. In thisstUdy, TSF has been evaluated for the rapid screeningof oils and soil extracts containing biodegraded crudeoil. Analysis of ten crude oils from the southern andwestern regions of the U.S. shows that theirfluorescence characteristics vary widely. Thesedifferences can be directly related to varying PAH com-position. TSF "fingerprints" of oil SUbjected tobioremediation for 52 weeks show systematicdifferences from those of the unaltered oils. Thesedifferences suggest that TSF can be used to measurethe abundance and composition of PAH's in samplesand to detect loss of PAH's in samples that have un-dergone biodegradation.

465

INTRODUCTION

Polynuclear aromatic hydrocarbons (PAH's) arenaturally occurring crude oil components. Although theconcentrations of PAH's in crude oils are relatively low,some 4-, 5-, and 6-ring PAH's are of potentialenvironmental interest because they have been found tobe mutagenic and/or carcinogenic at someconcentrations in laboratory studies. Table 1 shows thestructures and physiochemical properties of specificcrude oil PAH's [1].

Individual PAH compounds and i.somers vary widely intheir susceptibility to biodegradation. Degradationstudies of specific PAH's applied as pure chemicals tosoils have been conducted. From these studies,estimated first order half lives range from less than 12days for naphthalene to 347 days for benzo(a)pyrene[2,3].

Laboratory studies of biodegradation of PAH's in fossilfuel wastes [4], creosote-containing soils [5], and oilywaste-treated soils [6] show general trends in microbialdegradation. In general, a consistent trend ofdecreasing biodegradation with increasing ring numberis apparent. In a four month period, biodegradation ofPAH's in creosote-containing soil showed greater than90% loss for two ring PAH's, greater than 80% loss forthree ring PAH's, and between 0 and 60% loss for PAH'sof 4 or more rings.

2 Rapid Characterization of PAH's in Oils and Soils by Total Scanning Fluorescence SPE025990

The standard assessment of PAH's in oils, oily soils, andsludges requires solvent extraction, liquidchromatographic isolation of aromatic hydrocarbons,

. followed by identification and quantification using gaschromatography/mass spectrometry (GC/MS). Theexpense and labor intenSive nature of these analyticalmethods often limits routine PAH assessment of largenumbers of samples.

Fluorescence is an analytical technique that is selectivefor aromatic hydrocarbons. Oils contain a broad range ofaromatic compounds that exhibit fluorescence maximaat various emission/excitation wavelengths. Two-ringaromatic hydrocarbons such as naphthalene exhibit fluo-rescence maxima at low emission and excitationwavelengths, while five-ring compounds such asperylene have maxima at high emission and excitationwavelengths. Three and four ring compounds exhibitintermediate fluorescence characteristics. In contrast toconventional methods for PAH analysis, fluorescencecan be performed directly on oils or extracts with littlesample preparation.

Fixed wavelength fluorescence has been used since theearly 1970's as a supplemental geochemical indicator ingas surveys [7]. Total scanning fluorescence, whichprovides both a semi-quantitative estimate of fluores-cent aromatic compounds in a sample as well as an es-timate of their ring number distribution, has been usedto determine the concentration, distribution, and sourcesof aromatic hydrocarbons in sediments from the BeringStraits, the Gulf of Mexico, and the North Sea [8].

In a laboratory simulation of an oil spill [9], the totalscanning fluorescence spectra of biodegraded crude oilsamples showed little variation as a function ofincreasing biodegradation. The TSF "fingerprint" ofArabian crude oil had a high degree of similarity to thefluorescence spectra of oil residues after 121 days ofmicrobial alteration. However, these studies did notfocus on systematic or subtle changes in spectra whichmight be indicative of incipient biodegradation.Biodegradation of aromatic compounds by bacteria mayinitially involve side chain cleavage and oxidation of thering structure, which would produce limited spectralalteration. However, in cases of more extensivebiodegradation involving aromatic ring cleavage,spectral shifts should be notable.

In this study, TSF was evaluated for the rapid screeningof crude oils and soil extracts containing biodegradedcrude oil. To assess the compositional variability in TSF"fingerprints", ten crude oils from the southern andwestern regions of the U.S. were analyzed. The rela-tionship between the TSF "fingerprint" and theconcentration and distribution of specific PAH's deter-mined by GC/MS was then directly assessed. In

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addition, the ability to use total scanning fluorescence asa rapid and inexpensive tool flor predicting the extent ofbiodegradation in oily soils was investigated.

METHODS

Bulk chemical properties of tnn crude oils produced inthe southern and western mgions of the U.S. weremeasured using standard geoc:hemical techniques.

Three additional crude oils from a biodegradation studywere anaylyzed. Details of the bench-scalebiodegradation study are provided elsewhere [10]. Theobjective of the study was to assess the biologicalremoval of crude oil compommts spilled on soils. Theproject evaluated the biodegr,adation potential of threecompositionally-distinct Texas crude oils. The extent ofbiodegradation was monitored at discrete intervals overa 52-week period.

Polynuclear aromatic hydroccubons in both crude oilsand bioremediated soils were characterized by TSF andGC/MS. The total scanning fluorescence method is de-scribed in detail elsewhere [11]. Samples were pre-pared by quantitative dilution in hexane (7 ml). Thesample was introduced, via ;a cuvette, into a 650-40Perkin-Elmer micro-processor-controlled spec-trofluorometer. The excitation monochromator was setat a given wavelength and the emission monochromatorstepped from 200 to 500 nm. Resolution was 10 nmand the excitation wavelengths were varied from 200 to500 nm.

GC/MS analyses were performed using a Hewlett-Packard (HP) 5890A gas chromatograph and HP massselective (MSD) detector operated in the selected ionmonitoring mode (SIM). Chromatographic separationwas achieved using a 30-m long by 0.32-mm 1.0. fusedsilica capillary column with a DB-5 bonded phase. TheHP MSD was operated in the electron impact ionizationmode using an electron energy of 70 eV. This analysismeasures the concentrations of 2-ring through 5-ringPAH's in samples. In addition, total concentrations ofstructural homologues (compounds that have the samefundamental chemical structure but differ in thepresence of one or more additional carbon atoms) withincreasing degree of alkylation within several of the PAHseries are provided.

RESULTS

TSF and PAH Characteristics of Produced Oils

Concentrations of specific PAH's for the ten crude oils(designated "A" through "J") ,are shown in Table 2. Ingeneral, PAH distributions are dominated by 2- and 3-ring compounds, most notably naphthalene, fluorene

SPE025990 N. R. Gray, S. J. McMillen, J. M. Kerr, A. G. Requejo, G. Denoux, T. J. McDonald 3

and phenanthrene. These compounds are readilybiodegradable. Concentrations of 4- and 5-ring PAH's,the compounds of environmental interest, are less than10 parts per million (ppm) in most of the oils analyzed.Total concentrations of specific PAH's in the oils vary anorder of magnitude from 117 to 1174 ppm (Table 2).

TSF "fingerprints" of three oils varying widely in theirbulk chemical properties are shown in Figure 1. Oil 0, a27 API oil (upper figure) has a "fingerprint" dominatedby high emission and excitation wavelengths. The"fingerprint" of a 35.7 API oil (B) exhibits excitation andemission maxima at intermediate wavelengths (middlefigure). A 55.2 API condensate (H) has a TSF"fingerprint" dominated by low emission and excitationwavelengths (lower figure). Thus, the TSF characteris-tics of these oils vary roughly with their physicalproperties, with the lighter fluids exhibiting a shift towardlower emission/excitation wavelengths.

Bar diagrams depicting the PAH compositions of thesame three oils measured using GC/MS are shown inFigure 2. These diagrams illustrate the abundance of 2-through 5-ring PAH's and their alkyl homologues in theoils. Hence, for 2-ring aromatics, the concentration ofnaphthalene (N) is shown along with methylnaphthale-nes (C1 N), dimethylnaphthalenes (C2N), trimethylnaph-thalenes (C3N), and so on. Increasing alkylation withinthe phenanthrene, dibenzothiophene and chryseneseries is similarly shown. These data indicate thatconcentrations of alkylated homologues in crude oilsdominate over the parent ("un-alkylated") compoundsfor any individual PAH series.

Figure 2 shows that the PAH distribution of the 27 APIoil (D) is characterized by roughly equal abundance of2- and 3-ring aromatics and significant quantities of 4-ring aromatics. The 35.7 API oil (B) exhibits a signifi-cantly higher abundance of 2-ring relative to 3-ring com-pounds and lesser 4-ring PAH's, while the distribution ofthe 55.2 API condensate (H) is dominated by 2-ringcompounds. Comparison of these results with the TSFshown in Figure 1 indicates that high wavelength emis-sion/excitation fluorescence corresponds to a greaterabundance of 3- and 4-ring compounds. The TSF"fingerprints" of the other oils examined were variable,but in general reflected the overall trend shown inFigures 1 and 2. These data suggest that TSF canserve as a surrogate for more elaborate PAH analysesand is sensitive to changes in PAH composition, in par-ticular the relative abundance of 3- and 4-ring aromaticcompounds.

467

Bioremediation of Crude Oil in Soils

Table 3 shows bulk properties of crude oils used in thebioremediation studies (designated "K" through "M'lC15+ compositions of the oils show that oil K is a heavyasphaltic crude; oil M is more enriched in saturatedhydrocarbons, while oil L is intermediate in composition.Oil M was naphthenic, having undergone moderatebiodegradation in the reservoir.

The effect of bioremediation on the PAH composition ofeach of the three oils in soil will be discussedindiVidually. The composition of the oils following 52-weeks of incubation are discussed.

Crude Oil K

Figure 3 shows the PAH distribution of the oil K ischaracterized by a slight dominance of 2-ring over 3-ring compounds. Its TSF "fingerprint" is characteristic ofthe heavier oil shown earlier (oil D) with an enhancedhigh emission/excitation wavelength response (Figure3).

The PAH distribution resulting from 52 weeks ofbioremediation is also shown in Figure 3. Significantloss of PAH's is evident among the lower alkylhomologues of the 2- and 3-ring compounds. Some ofthe loss of naphthalenes could be due to volatile losses.However, loss of 3-ring PAH's, which are lesssusceptible to volatile losses, is clearly evident. Thegreater susceptibility of lower alkyl homologue PAH's tobiodegradation has been reported in earlier studies[9,12]. The TSF "fingerprint" of the oil clearly changesas a result of biodegradation, exhibiting a shift towardlower emission/excitation maxima (Figure 3). Thissuggests that TSF may be suitable as a inexpensivescreen for PAH degradation in bioremediated soils.

Crude Oil L

The PAH composition of the intermediate oil as de-termined by GC/MS is similar to that of oil K (Figure 4).However, its TSF "fingerprint" differs, exhibiting lowerresponse at high emission/excitation wavelengths and afluorescence maxima at lower emission/excitation wave-lengths. After 52 weeks of bioremediation (Figure 4) thePAH composition of oil L showed the fewest changes.Only slight degradation of the lower alkyl homologuesamong the 2-ring and 3-ring compounds is evident(Figure 4). Nevertheless, the TSF "fingerprint" of thebiodegraded oil (Figure 4) has been affected in thesame manner as oil K. showing a decreased response inhigh emission/ excitation fluorescence wavelengths anda slight shift toward lower wavelength maxima. Thissuggests that TSF is sensitive even to subtle changes inPAH composition resulting from biodegradation.

4 Rapid Characterization of PAH's in Oils and Soils by Total Scanning Fluorescence SPE025990

Crude Oil M

The PAH distribution of the lighter oil M consistsprimarily of 2-ring PAH's and contains a lower relativeabundance of 3-ring PAH's (Figure 5). Its TSF"fingerprint" is shifted slightly toward lower fluorescenceemission/excitation wave-lengths in comparison to theother two oils (Figure 5). Bioremediation of oil M re-sulted in significant loss of lower alkyl homologues ofnaphthalenes as well as some of the f1uorenes,phenanthrenes and biphenyls. The TSF "fingerprint" ofthe biodegraded soil extract, however, was littlechanged from that of the original oil (Figure 5). This islikely due to the fact that the PAH's in this oil consistedprimarily of 2-ring compounds. TSF is more sensitive tochanges in abundance of 3-ring and 4-ring compounds,which are lesser constituents of oil M. Also, oil M hadalready undergone biodegradation (in the reservoir) priorto bioremediation. Biodegradation of PAH's maytherefore have occurred prior to bioremediation suchthat, under the conditions employed, further degradationwas not readily discernible using TSF.

COMPARISON OF RESULTS

Concentration of specific PAH's in the three oils beforeand after degradation are shown in Table 4. Selectivedegradation of the parent PAH's, such as naphthalene,gives the appearance that the concentrations havedeclined significantly. However, a lesser extent ofbiodegradation is indicated when the alkyl homologues,the C1-C4 naphthalenes,are included. Total concentra-tions decrease primarily as a result of the nearlycomplete loss of naphthalene. Naphthalene loss in thesoil extracts may be in part be due to volatile lossesovertime.

These results indicate that TSF is suitable as aninexpensive technique for monitoring changes in PAHcomposition of soils containing biodegraded crude oil. Itis effective in distinguishing biodegraded oils from theirunaltered equivalents. The potential for characterizingdifferences in the degree of biodegradation using TSF"fingerprints" is under investigation.

CONCLUSIONS

Polynuclear aromatic hydrocarbons (PAH's) arenaturally occurring crude oil components. The standardanalytical methods for measuring PAH's in oils, oilysoils, and sludges are labor intensive and costly, limitingroutine PAH assessment of large numbers of samples.In this study, total scanning fluorescence was evaluatedfor the rapid screening of crude oils and soil extractscontaining biodegraded crude oil.

468

The results show that TSF is s,ensitive to differences inPAH composition in a variety of produced oils from thewestern and southwestern U.S. These data indicate thatTSF can be used to "fingerprint" the PAH distribution ofoils and thereby serve as a surrogate for more expen-sive PAH analyses.

The crude oils in this study were dominated by 2- and 3-ring compounds. The concentrations of 4- and 5-ringcompounds which may be of potential environmentalconcern are less than 10 ppm in most of the oilsanalyzed.

In a study of the effect of bioremediation on the PAHcomposition of different oils, T'SF reflects changes thataccompany PAH degradation. These changes consistprimarily of the loss of lower homologues within the 2-and 3-ring aromatic series and are accompanied by adecrease in high emission/excitation wavelengthresponse within TSF "fingerprints". The results suggestthat TSF can be used to monitor changes in PAHcomposition of biodegraded crude oil. It is mosteffective in distinguishing biodegraded oils and theirunaltered equivalents.

ACKNOWLEDGMENTS

The authors wish to thank Exxon Production ResearchCompany for permission to pUblish the results of thisstudy.

REFERENCES

1. Sims, R. C. and Overcash, M. R. "Fate ofPolynuclear Aromatic Compounds (PNAs) in soil-plantsystems," Residue Reviews, Vol 88 (1983).

2. Bulman, T. L., Lesage, S., Fowlie, P. J. A., andWebber, M. D. "The Persisten

SPE025990 N. R. Gray, S. J. McMillen, J. M. Kerr, A. G. Requejo, G. Denoux, T. J. McDonald 5

6. Cansfield, P. E., and Racz, G. J. "Degradation ofHydrocarbon Sludge in the Soil," Can. J. Soil Sci., Vol58 (1978).

7. Horvitz, L. "Geochemical Exploration for Petroleum,"Science, Vol 229 (1985)

8. Brooks, J. M., Kennicutt, M. C., and Carey, B. D."Offshore Surface Geochemical Exploration," Oil andGas Journal, Vol 84 (1986).

9. Kennicutt, M. C'. "The Effect of Biodegradation onCrude Oil Bulk and Molecular Composition," Oil andChemical Pollution, Vol 4 (1988).

10. McMillen, S. J., Kerr, J. M., Gray, N. R,"Bioremediation of Crude Oils in Soil," Paper SPE025981 presented at the 1993 SPElEPA Exploration &Production Environmental Conference, San Antonio,March 7-10.

11. Brooks, J. M., Kennicutt, M. C., Barnard, L. A., andDenoux, G. J. "Application of Total ScanningFluorescence to Exploration Geochemistry," Proc.Offshore Technology Cont. No. 15, Vol 1 (1983)

12. Rowland, S. J., Alexander, R, Kagi, R I., Jones, D.M., and Douglas, A. G. "Microbial Degradation ofAromatic Components of Crude Oils: A Comparison ofLaboratory and Field Observations," Org. Geochem, Vol9 (1986).

Table 1. Structures and PhysicalChemical Properties of PAH's (1)Structure Aqueous Vapor Pressure(No. of mpa bpb solubility log (torr at

PAH Rings) DC DC (mg/L) Kn C 20C)Naphthalene 2 80 218 30 3.37 4.92 x 10'"Acenaphthene 3 96 279 3.47 4.33 2.0 x 10.2Acenaphthylene 3 92 265 3.93 4.07 2.9 x 10.2Anthracene 3 216 340 0.07 4.45 1.96 x 10.4Phenanthrene 3 101 340 1.29 4.46 6.80 x 10.4Fluorene 3 116 293 1.98 4.18 1.3 x 10.2Fluoranthene 4 111 ._. 0.26 5.33 6.0 x 10.6Benz(a)anthracene 4 158 400 0.014 5.61 5.0 x 10.9Chrysene 4 255 ... 0.002 5.61 6.3 x 10.7Pyrene 4 149 360 0.14 5.32 6.85 x 10.7Benz(a)pyrene 5 179 496 0.0038 6.04 5.0 x 10.7Benzo(b)nuoranthene 5 167 ... 0.0012 6.57 5.0 x 10.7Benzo(k)nuoranthene 5 217 480 0.00055 6.84 5.0 x 10.7Dibenz(a,h).anthracene 5 262 .- 0.0005 5.97 1.0 x 10.10Benzo(ghi)perylene 6 222

--0.00026 7.23 1.0 x 10.10

Indeno(1,2,3-cd) pyrene 6 163--

0.062 7.66 1.0 x 10.10

~mp = melting POintbp = boiling point

c 10gKp = logarithm of the octanol:waler partition coefficient

Table 2. Concentrations of PAH's in Oils from the Western and Southwestern U.S.

CRUDE OILS (Units: m9/k9 of 011)A B C D E F G H I J

API API API Gravity:GravIty: GravIty: 55.2

35.7 270

PAHNAPHTHALENE 67.6 584 6801 064 166.3 7541 217.4 108.0 141.3 882.0ACENAPHTHYLENE 07 03 0.8 02 07 1.3 05 0.5 0.5 1.1ACENAPHTHENE 6.3 2.9 7.4 1.9 58 80 89 40 3.9 17.0FLUORENE 16.0 16.3 838 39 20.0 435 14.5 22.4 33.5 107.2PHENANTHRENE 28.4 25.2 1522 318 396 1513 136 37.8 56.1 124.2ANTHRACENE 4.2 20 122 2.4 3.4 12.9 NO 1.8 5.9 5.9FLUORANTHENE 2.0 0.4 29 0.9 1.9 14 01 05 12 6.5PYRENE 38 28 118 10 44 8.5 1.4 2.8 58 8.8BENZaANTHRACENE 2.4 15 412 22 21 108 05 NO 22 4.4CHRYSENE 41 4.8 5.6 106 7.7 212 07 30 92 9.5BENZObFLUORANTHENE 06 06 2.3 1 1 1.1 14 0.2 06 0.9 2.5BENZOkFLUORANTHENE 03 0.4 23 0.9 0.7 1.4 02 01 0.5 14BENZaPYRENE 05 03 2.8 10 15 14 02 02 11 1.2INOEN0123cdPYRENE 0.4 05 07 02 05 02 02 01 0.1 06OIBENZahANTHRACENE 0.3 04 17 12 04 10 03 0.3 0.8 07BENZOQhlPERYLENE 0.4 05 27 10 06 1.6 02 0.3 19 1 3

Total 1380 1173 10105 1267 2567 10200 2589 182.4 2649 1174.3

469

6 Rapid Characterization of PAH's in Oils and Soils by Total Scanning Fluorescence

Table 3. Bulk properties of oils and soils used in biodegradation experiments;.

CRUDE OILSK L M

C15+ Composition of Oils (O/OJ:Saturated Hydrocarbons 35 46 67

Aromatic Hydrocarbons 34 34 26

Heterocompounds 12 12 4

Asphaltenes 19 8 3

Table 4. Concentrations of PAH compounds in crude oils before and after 52 weeks bioremediation.

K L M il*~:::~. K L ~gInitial ~~ili~1~~~ (52 Weeks)

(Units mglkg of oil) ~~~~~~~~~~BNAPHTHALENE 441.6 767.3 438.9 0.4 0.9 ().4ACENAPHTHYLENE 0.6 2.6 0.1 0 0 Cl.1

ACENAPHTHENE 9.4 15.7 27.3 0.6 4.4 11.6

FLUORENE 16.2 106.2 75.5 1.9 38.8 Cl.8

PHENANTHRENE 60.9 216.9 96.5 1.1 108.5 (1.7ANTHRACENE 5.7 23.7 2.1 2 11.5 (1.6FLUORANTHENE 3.5 6.1 8.5

::.4.7 1:.6:::::

PYRENE 5.3 12 6.9 :~riliMf 2.6 15.2 ~1.7:::::::::-;$:::.

BENZaANTHRACENE 4.1 3 1.9 I 4.7 1.3 1.1CHRYSENE 15.7 22.3 9 12.7 7.8 "'~.7BENZObFLUORANTHENE 1.7 2.3 0.5 1.4 0.8 0.4BENZOkFLUORANTHENE 1.8 2.3 0.5 ~ 1.4 0.8 CI.4BENZaPYRENE 0.8 0.6 1.1 0.4 0.5 CI.4INOEN0123cdPYRENE 2 0.8 0.3 0.1 CI.1OIBENZahANTHRACENE 2.5 2.3 1.5 0.3 0.1 CI.1::BENZOghiPERYLENE 4.4 1.5 1.7 :~: 1.1 0.4 CI.1

Total 14.8

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SPE025990

SPE025990 N. R. Gray, S. J. McMillen, J. M. Kerr, A. G. Requejo, G. Denoux, T. J. McDonald 7

INT450360270

180

90

o500

450400

350400 300450 ,250 EX

500200EM

E2026. 82 EPR Oil "0" 10 PPM28-NDV-92 .0 GRINT MAX = 447[430 (EM)/380(EX)]R1 = 2.529127

T1 = 80354.6 T2 = 59435.6

E2016. 82 EPR Oil "8" 10 PPM1-DEC-92 .0 GR

INT MAX = 607[380 (EM)/330(EX)]R1 = 3.159837

INT610488

366244

122

o500450

350400

E" 400, 300 EX'" 450 250500200T1 = 79593.9 T2 = 62876.9

52

EX

~~.... O500

450400350

400 300450500'200250EM

E2046. 82 EPR Oil "H" 10 PPM28-NDV-92 .0 GR INTINT MAX = 255[340 (EM)/280 (EX)]

[260

R1 = .692674208

I~156L104I

T1 = 12200.8 T2 = 11869.0

Figure 1. TSF "Fingerprints" of 3 Compositionally Diverse Oils

471

8Rapid Characterization of PAH's in Oils and Soils by Total Scanning Fluorescence

S-Ring+4-Ring

3-Ring2-Ring

SPE025990

350300250

1'& 200~ ~ 150f ~!~ 100

50o

45040035030025020015010050o

~~~~f5-Ring+4-Ring

3-Ring--Ring

5-Ring+4-Ring

3-Ring2-Ring

Figure 2. PAH Compositions of the Same Three Oils Shown in Figure 1.

472

SPE025990 N. R. Gray, S. J. McMillen. J. M. Kerr, A. G. RequeJo, G. Denoux, T. J. McDonald 9

150

INT

[

750

600450

300

EX

79318.0T2

EM

o2002:: 0, 450

500300' 400-~O' 350~~ 400' 300

450 250500200

16-DEC-92 .~ GR1NT MAX = 7~5[390 (EM)/330 (EX)];:d = 3.891921

i1 = 99643.2

,..620

1NT_102::

~615,

L41 G'\~205

118019.7T2

Lc200 /""::00

250_ 0 450-0 400~ 350 350

EM 4004 0 250300 EX

5 500200T1 = 161878.8

11-DEC-92 .0 GRINT MAX = 1020[420 (EM)/370(EX)]Rl = 3.460667

. Initial Oil K Soil Extract After 52 Weeks

1000900800700600500400300200100

o

PAH Alkyl Homologue

Figure 3. TSF "Fingerprints" (Upper) and PAH Compositions (Lower) of Oil K and Soil Extract After 52 WeeksBioremediation

473

10 Rapid Characterization of PAH's In Oils and Salls by Total Scanning Fluorescence SPE025990

1-G~C-~~ .J GRNT ~AX = S61 [390 (EM)/330 (EX)]1 = 2.301539

69776.1T2

EM

i6-DEC-~2 .0 GRINT MAX = 677[380 (EM)/330(EX)]'11 = 1.825286 r Q80

I

: 544

r408r

t:::200 10J~~~-...10

250 500300 450350 350400

400450 ~50300 EX500200'"

T1 = 82746.6T2 = 72364.4

INT_665iL5321 399[266I

I n3r--\. 0

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300350 _00350400400. 250.:1 EX

EM 450500'200T1 = 89248.2

Initial Oil L Soil Extract After 52 Weeks

200018001600140012001000

800600400200

o

PAH Alkyl Homologue

5-Ring+

Figure 4. TSF "Fingerprints" (Upper) and PAH Composition (Lower) of Oil L and Soil Extract After 52 WeeksBioremediation

474

SPE025990 N. R. Gray, S. J. McMillen, J. M. Kerr, A. G. Requejo, G. Denoux. 1. J. McDonald 11

INTr 765

l6121 459r306

T2 = 70893.7

153

o500

450350400

,. EM 400450500 200250300 EX

16-0EC-92 .0 GRINT MAX = 760[360 (EM)/300 (EX)]Rl = 2.632382

Tl = 85068.7

INT

T2 = 44181.7

EM

r440~352~264II 176

[88o

200' 500250 450

300 400350400, 300350

450 250 EX500200

l1-DEC-92 .0 GRINT MAX = 437[360 (EM)/300 (EX) ]Rl = 1.952756

T1 = 53309.3

Initial Oil M Soil Extract After 52 Weeks

2500

2000

1500

1000

500

PAH Alkyl Homologue

'40

120

100

80

Figure 5. TSF "Fingerprints" (Upper) and PAH Composition (Lower) of Oil M and Soil Extract After 5f WeeksBioremediation

475

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