Polycyclic ar o matic hy dro car bons in crude oils from Po land
Izabela BOJAKOWSKA and Gertruda SOKOŁOWSKA
Bojakowska I. and Sokołowska G. (2001) — Polycyclic ar o matic hy dro car bons in crude oils from Po land. Geol. Quart., 45 (1): 81–86.
Warszawa.
The con tent of 17 polycyclic ar o matic hy dro car bons (PAHs) in oil sam ples de rived from all three oil-bearing re gions of Po land, i.e. from the Carpathians, the Carpathian Foredeep and the Pol ish Low lands (the Fore-Sudetic-Wielkopolska, the West ern Pom er a nian and the Peribaltic ar eas), were de ter mined. The con cen tra tions of PAHs de ter mined in these crude oils var ied from 22.85 to 332.45 ppm. The av - er age con tent of PAHs in crude oils from the Carpathians and the Carpathian Foredeep (191.18 ppm) was sev eral times higher than that in crude oils from the Pol ish Low lands (44.70 ppm); there was through out, though, a rel a tively small vari abil ity in the con tent of perylene, vary ing from 0.50 to 0.80 ppm. Of PAH com pounds de ter mined, the larg est share was oc cu pied by 3-cyclic hy dro car bons (an av er age of 72%) and 4-cyclic (about 24%), whereas the con tent of 5- and 6-cyclic hy dro car bons did not ex ceed 3%. Phenanthrene and fluorene were pre vail ing PAH com pounds. The di verse PAH com po si tion in oil sam ples from the Pol ish Low lands com pared to those from the Carpathians and the Carpathian Foredeep seems to have re sulted more from the com po si tion of orig i nal or ganic mat ter than from the course of geo chem i cal and bio chem i cal pro cesses (which oc cur dur ing bio mass de cay) and the sub se quent mi gra tion of these com pounds in rock for ma tions.
Izabela Bojakowska and Gertruda Sokołowska, Pol ish Geo log i cal In sti tute, Rakowiecka 4, PL-00-975 Warszawa, Po land; e-mail:
iboj@pgi.waw.pl (re ceived: July 15, 1999; ac cepted: De cem ber 2, 2000).
Key words: polycyclic ar o matic hy dro car bons, crude oils.
INTRODUCTION
The polycyclic ar o matic hy dro car bons (PAHs), many of which pos sess toxic, mutagenic and car ci no genic prop er ties, are pol lut ants com monly pres ent in small amounts in all en vi - ron men tal sys tems (McGroddy and Farrington, 1995; Ollivon et al., 1995; Maliszewska-Kordybach and Terelak, 1996;
Bojakowska and Sokołowska, 1998; Harvey, 1998). Some of these polyarenes pres ent in the en vi ron ment are of nat u ral or i - gin; they oc cur in plants or are the prod ucts of met a bolic pro - cesses in mi cro or gan isms that de com pose or ganic re mains; in ad di tion, they orig i nate dur ing geo chem i cal and bio chem i cal pro cesses that lead to the for ma tion of fos sil fu els (in clud ing crude oil gen er a tion) or are syn the sised dur ing vol ca nic erup - tions, and for est, bush and peat fires (Ev ans et al., 1990;
Capaccioni et al., 1995; Jiang et al., 1998; Koziński and Saade, 1998; Harvey, 1998; Howsam and Jones, 1998). How ever, most PAHs in re cent soils and sed i ments orig i nate from
anthropogenic sources, particularly as the re sult of burn ing fu - els for do mes tic, in dus trial and trans port needs, coal cok ing and oil treat ment, and steel and alu mi num man u fac tur ing. PAHs also reach the en vi ron ment via liq uid fuel spills dur ing trans - port, stor ing or car han dling (Behymer and Hites, 1988;
Harvey, 1998; Howsam and Jones, 1998).
Polycyclic ar o matic hy dro car bons oc cur in the en vi ron - ment as a mix ture of com pounds con tain ing two or more ar o - matic (ben zene) rings. Their par tic u lar com po si tion var ies ac cord ing to rock and sed i ment type. The great est haz ard is caused by high mo lec u lar com pounds, es pe cially by those con - tain ing five or more rings. These harm and de grade slowly in the en vi ron ment, and so ac cu mu late in soils and re cent sed i - ments. If the com po si tion of a PAH mix ture in fos sil fu els is af - fected by the com po si tion of orig i nal ma te rial, the depositional con di tions (pH, Eh, tem per a ture), the course of bio chem i cal pro cesses dur ing or ganic de cay and the course of carbonification and hy dro car bon gen er a tion af ter burial, the
PAH com po si tion in re cent soils and sed i ments is largely linked to the prod ucts of burn ing re leased to the at mo sphere.
Crude oils gen er ally con tain sev eral per cent age of PAHs, with sub sti tuted naph tha lene and phenathrene be ing prev a lent.
The pro por tion of unsubstituted PAH is rel a tively small; in gen eral, crude oils are char ac ter ised by a very low con tent of 5- and 6-cyclic ar o matic hy dro car bons of this type (Bence et al., 1996). The high est con cen tra tions of high mo lec u lar PAHs (about sev eral hun dreds ppm) were re corded in hy dro ther mal oils in the Gulf of Cal i for nia; these were gen er ated by al ter ation of or ganic mat ter at tem per a tures of 260–350oC (Simoneit and Fetzer, 1996). The prev a lence of 4-, 5- and 6-cyclic ar o matic hy dro car bons over 2- and 3-cyclic ones, and com pounds unsubstituted over alkylated compounds is also char ac ter is tic for prod ucts of oil com bus tion as op posed to non-combusted oils (Bence et al., 1996). Of the PAH mix ture con tained in ex - haust gases, about 50% be long to com pounds which “sur - vived” com bus tion, even though the “sur vival rate” of in di vid ual PAH com pounds dur ing burn ing var ies from 0.04 to 0.87% (Beak et al., 1991; Tancell et al., 1995; Howsam and Jones, 1998).
There is lit tle in for ma tion on the oc cur rence of en vi ron - men tally im por tant PAHs in fos sil fu els. The abun dant lit er a - ture on the or ganic chem is try of an cient en vi ron ments deals mostly with alkylated PAHs such as methylphenathrenes, good mark ers that en able de ter mi na tions of oil ma tu rity and its source of or i gin (Pu et al., 1990; Ramanampisoa and Radke, 1995; Smith et al., 1995; Requejo et al., 1996). Yet knowl edge of the ranges in con cen tra tion of high mo lec u lar PAHs in crude oils is es sen tial be cause oil ex ploi ta tion, trans port, stor ing and pro cess ing, as well as com bus tion of crude oils and their de riv - a tives, are a sig nif i cant source for re leas ing these com pounds to
the en vi ron ment. There has been a lack of in for ma tion on the con cen tra tions of unsubstituted PAHs in crude oils from Pol ish de pos its.
SCOPE AND METHODS OF INVESTIGATION
The con tent of PAHs was de ter mined in 30 sam ples of crude oils de rived from all three oil-bearing re gions of Po land, i.e. from the Carpathians, the Carpathian Foredeep and the Pol - ish Low lands (the Fore-Sudetic-Wielkopolska, the West ern Pom er a nian and the Peribaltic ar eas).
In the Carpathians 18 sam ples from de pos its, lo cated in the Silesian and the Subsilesian units, were ex am ined. These sam - ples were de rived from the fol low ing de pos its: Krościenko, Potok-Turaszówka and Bóbrka-Rogi in which oil-bear ing ho - ri zons oc cur within the Ciężkowice Sand stones, Iwonicz-Zdrój and Osobnica the oils of which oc cur within the Ciężkowice and the Istebna Sand stones, and Wola Jasienicka in which oil-bear ing ho ri zons oc cur within Early Cre ta ceous rocks, i.e.
the Węglowice Marls and Sand stones (Depowski, 1987).
These crude oils were gen er ated pri mar ily from or ganic mat ter con tained in Late Cre ta ceous and Ter tiary host rocks (ten Ha - ven et al., 1993). In the Carpathian Foredeep 3 oil sam ples from the Grobla-Pławowice de posit lo cated north of Bochnia were ex am ined. In this de posit crude oil has ac cu mu lated in Cenomanian sand stones and Oxfordian lime stones. In the West ern Pom er a nian area 3 oil sam ples (from the Rekowo, Kamień Pomorski and Wysoka Kamieńska de pos its) and in the Fore-Sudetic-Wielkopolska area 4 sam ples (from the Jeniniec, Górzyca, Kije and Kosarzyn de pos its) were in ves ti gated. Oil de pos its in the Fore-Sudetic-Wielkopolska and the West ern Pom er a nian ar eas re late to the Zechstein Main Do lo mite; hy - dro car bons gen er ated from this lithostratigraphic unit are re - cog nised as autochthonous (Karnkowski, 1993). In the Łeba El e va tion of the mid dle Peribaltic area, where oil-bear ing ho ri - zons oc cur in the up per part of Mid dle Cam brian quartz sand - stones, 2 oil sam ples from the Żarnowiec-Dąbki de posit were stud ied (Karnkowski, 1993). The lo ca tion of these sam pled oil de pos its is shown in Fig ure 1.
In oil sam ples de rived from these de pos its 17 PAHs, i.e.
acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benzo(a)anthracene, chry - sene, benzo(b)fluoranthene, benzo(k)fluoranthene, benzo(e)pyrene, benzo(a)pyrene, perylene, indeno(1, 2, 3-cd)pyrene, dibenzo(ah)anthracene, benzo(ghi)perylene, are listed in en vi ron men tal stud ies by the US EPA (US En vi ron - men tal Pro tec tion Agency). The frac tion of ar o matic hy dro car - bons was ob tained us ing a co lum nar chro ma tog ra phy method (Al2O3, SiO2). The anal y ses were per formed us ing a Hewlett Packard gas chromatograph type 5890 II with a mass spec - trom e ter GS-MSD 5981 de tec tor. A HP-5 non-polar cap il lary col umn (length — 25 m, di am e ter — 0.2 mm, film — 0.33 µm) (5%)-diphenylo -(95%)-dimethylopolysiloxane was ap plied.
The tem per a ture was set from 70 to 200°C with a rate of 10°C/min and from 200 to 300°C with a rate of 2.5°C/min. The
Fig. 1. Lo ca tion of crude oil de pos its sam pled
T a b l e 1 PAHs in crude oils of dif fer ent re gions from Po land (ppm)
Hy dro car bons Carpathians and Carpathian Foredeep
regions (n = 21)
Pol ish Low lands (Sudetic-Wielkopolska and West ern Pom er a nian ar eas)
(n = 7)
Łeba El e va tion (n = 2)
Acenaphthylene (Ace) <0 15−3 97∗
1 29
. .
.
<0 15−1 56 0 74
. .
. < 0.15
Acenaphthene (Acf) <0 15−7 04 2 47
. .
.
<0 15−0 80 0 39
. .
. < 0.15
Fluorene (Fl) 7 25 83 94
31 37
. .
.
− 2 25 14 38
8 60
. .
.
− 1 86 6 48
4 17
. .
.
−
Phenanthrene (Fen) 48 59 175 18
102 42
. .
.
− 13 72 26 71
21 26
. .
.
− 16 16 38 86
27 51
. .
.
−
Anthracene (Ant) 0 98 3 37
1 75
. .
.
− 0 58 1 92
1 23
. .
.
− 0 33 0 92
0 63
. .
.
−
Fluoranthene (Flu) 2 33 8 52
4 70
. .
.
− 0 08 0 79
0 41
. .
.
− < 0.15
Pyrene (Pir) 4 14 18 92
11 04
. .
.
− 0 69 3 56
2 04
. .
.
− 113 3 72
2 43
. .
.
−
Benzo(a)anthracene (BaA) 1 01 7 19
3 47
. .
.
− <0 23−1 09
0 27
. .
. < 0.23
Chry sene (Ch) 7 48 51 28
27 18
. .
.
− 2 02 26 30
8 29
. .
.
− 6 51 14 43
10 47
. .
.
−
Benzo(b)fluoranthene (BbF) 0 30 2 79 0 94
. .
.
− <0 05−0 22
0 09
. .
.
0 19 0 31 0 25
. .
.
−
Benzo(k)fluoranthene (BkF) < 0.05 < 0.05 < 0.05
Benzo(e)pyrene (BeP) 0 36 10 66
3 12
. .
.
− <0 05−1 25
0 40
. .
.
0 49 3 52 2 01
. .
.
−
Benzo(a)pyrene (BaP) <0 05−1 22 0 43
. .
.
< −
<
0 05 0 12 0 05
. .
.
<0 05−0 29 0 16
. .
.
Perylene (Per) 0 31 117
0 65
. .
.
− 0 52 0 77
0 62
. .
.
− 0 52 0 56
0 54
. .
.
−
Indeno(1, 2, 3-cd)pyrene (IndP) <0 10−0 41 0 10
. .
. < 0.10 < 0.10
Dibenzo(ah)anthracene (DahA) <0 10−0 74 0 14
. .
.
< −
<
0 10 0 12 0 10
. .
. < 0.10
Benzo(ghi)perylene (Bper) <0 10−0 93 0 14
. .
.
<0 10−0 41 0 12
. .
.
<0 10−0 31 0 18
. .
. To tal PAHA
71 05 245 25 139 29
. .
.
− 17 75 43 77
32 22
. .
.
− 18 50 46 41
32 46
. .
.
− To tal PAHB
18 42 77 41 46 38
. .
.
− 3 81 28 28
11 01
. .
.
− 7 83 18 34
13 08
. .
.
− To tal PAHC
1 29 16 39 5 50
. .
.
− 0 84 2 55
1 40
. .
.
− 1 39 5 11
3 25
. .
.
− To tal PAH17 = PAHA + PAHB +
PAHC
91 76 332 45 191 20
. .
.
− 22 85 68 55
44 70
. .
.
− 27 77 69 89
48 83
. .
.
−
∗min. content−max. content
mean value ; to tal PAHA — to tal of 3-cyclic ar o matic hy dro car bons [acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene]; to tal PAHB — to tal of 4-cyclic ar o matic hy dro car bons [fluoranthene, pyrene, benzo(a)anthracene, chry sene];
to tal PAHC — to tal of 5- and 6-cyclic ar o matic hy dro car bons [benzo(b)fluoranthene, benzo(k)fluoranthene, benzo(e)pyrene, benzo(a)pyrene, perylene, indeno(1, 2, 3-cd)pyrene, dibenzo(ah)anthracene, benzo(ghi)perylene]
anal y ses were per formed us ing an outer stan dard method; the fol low ing stan dards were ap plied: PM-612 from ULTRA Sci - en tific or cer ti fied perylene and benzo(a)pyrene. The sam ples were ana lysed at the Cen tral Chem i cal Lab o ra tory of the Pol ish Geo log i cal In sti tute.
RESULTS AND DISCUSSION
In the crude oils ex am ined de rived from these Pol ish de pos - its of dif fer ent ages, the to tal con tent of 17 PAHs var ied from 22.85 to 332.45 ppm (Tab. 1). The crude oils from de pos its of the Fore-Sudetic-Wielkopolska, the West ern Pom er a nian and the mid dle Peribaltic ar eas, as well as from de pos its of the Carpathians and the Carpathian Foredeep, showed dis tinct dif - fer ences (Fig. 2). The crude oils from the Carpathians and the Carpathian Foredeep de pos its, linked to Caino zo ic and Me so - zoic flysch rocks, were char ac ter ised by an av er age con tent of PAHs (191.20 ppm), which was four times higher com pared to those de rived from Palaeozoic rocks of the Pol ish Low lands (44.70 ppm).
Of the 3-cy clic ar o matic hy dro car bons ex am ined (acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene), phenanthrene and fluorene showed the high est con cen tra tions, whereas acenaphthylene the low est. The crude oils from the Carpathians showed much higher con cen tra tions of these hy dro car bons (phenanthrene — 102.42 ppm and fluorene — 31.37 ppm) com pared to those from the Pol ish Low lands con tain ing 21.26 and 8.6 ppm, re spec tively (Tab. 1).
By com par i son, the crude oils in the Alaska North Slope pipe - line com ing from the oil fields of Prudhoe Bay, Kuparuk, Endicott and Lisburne, re lated to Tri as sic-Cre ta ceous shales, were fea tured by higher lev els of phenanthrene (262.5 ppm) and fluorene (92.9 ppm) (Bence et al., 1996). In the Pol ish crude oils, 3-cy clic ar o matic hy dro car bons were dom i nant, reach ing about 72% of the to tal PAHs. The low est share of
these hy dro car bons was re corded in crude oils from the Wysoka Kamieńska bore hole (Pol ish Low lands), reach ing 56.3%, and in those from the Pławowice de posit (Carpathian Foredeep) — 61.5–65.5%. Among the PAHs de ter mined, phenanthrene was nearly con stant con sti tut ing 53±6% of the to tal 17 com pounds ex am ined.
Of 4-cy clic ar o matic hy dro car bons [fluoranthene, pyrene, benzo(a)anthracene, chry sene] de ter mined, chry sene showed the high est con cen tra tions, and benzo(a)anthracene the low est.
Con sid er ably higher av er age lev els of these com pounds (46.38 ppm) were re corded in crude oils of the Carpathians and the Carpathian Foredeep com pared to those from the Pol ish Low - lands (11.0 ppm). The Carpathian Foredeep oils also had a lower con tent of fluoranthene than did the Carpathians oils (Tab. 1). The 4-cy clic ar o matic hy dro car bons formed on av er - age of 24% of the to tal PAHs. The high est pro por tion of these com pounds was re corded in the Wysoka Kamieńska bore hole (Pol ish Low lands) (41.3%) and from the Pławowice de posit (Carpathian Foredeep) (29.0–32.6%), and the low est in the crude oils of the Górzyca (16.7%) and Kosarzyn (15.3%) bore - holes in the Pol ish Low lands.
Of 5- and 6-cyclic ar o matic hy dro car bons, benzo(a)pyrene and benzo(b)fluoranthene showed the high est con cen tra tions.
The con tent of benzo(k)fluoranthene in the crude oils ex am - ined was be low de tec tion lim its, whereas indeno(1, 2, 3-cd)pyrene and dibenzo(ah)anthracene were re corded only in crude oils from the fol low ing: Bóbrka-Rogi (Carpathians), Pławowice (Carpathian Foredeep), Górzyca (Pol ish Low - lands). The high est lev els of 5- and 6-cyclic com pounds were noted in crude oils of the Carpathians de pos its at Grobla and Bóbrka. Most of the ex am ined Carpathians crude oils con - tained benzo(b)fluoranthene (av er age 0.94 ppm) and benzo(a)pyrene (0.43 ppm), whereas in Zechstein crude oils of the Pol ish Low lands, these com pounds were com monly be low de tec tion lim its. In all the oil sam ples ex am ined perylene showed rel a tively small vari a tion; its con tent in most sam ples
Fig. 2. PAHs in crude oils from dif fer ent oil-bearing ar eas of Po land For ex pla na tions see Ta ble 1
var ied from 0.50 to 0.80 ppm. Perylene, a com pound formed as a re sult of bi otic and abiotic trans for ma tion of or ganic mat ter, is re garded as an in di ca tor of anoxic sed i men tary en vi ron ments (Silliman et al., 1998). The 5- and 6-cyclic ar o matic hy dro car - bons de scribed make up only about 2.6% of the to tal PAH con - tent in the crude oils ex am ined.
The ob served vari a tion in PAH con tent was pri mar ily caused by orig i nal or ganic com po si tion. Hy dro car bons ac cu - mu lated in rocks of the Main Do lo mite (in clud ing the Wysoka Kamieńska and Kamień Pomorski de pos its) were pro duced from sapropelic or ganic mat ter (kerogen) of type II (Kotarba et al., 1998), whereas those in Carpathian flysch rocks in clude humic or ganic mat ter (kerogen of type III) (Czepiec and Kotarba, 1998). Pri mary dif fer ences may have been con nected not only with the dif fer ent chem i cal com po si tions of terrestrial and marine plants, but also with plant tax o nomic differences in successive geo logic eras.
Al though the crude oils ex am ined are char ac ter ised by much higher con cen tra tions of PAHs com pared to those from solid fos sil fu els (their con cen tra tions in crude oils run to tens or more ppm, whereas in peats there are hun dreds ppb, and, in brown and hard coals, sev eral ppm), they con tain much less perylene than brown coals, and less benzo(a)pyrene than hard coals (Bojakowska and Sokołowska, 1999).
The pro por tion of in di vid ual com pounds in the over all PAH com po si tion is in ter est ing. A nearly con stant level of
perylene in the PAH mix ture ex am ined was ob served; this pre - vail ing PAH com pound con sti tutes gen er ally 53±6% of the to - tal PAHs. In ad di tion, a greater share of high mo lec u lar com pounds, i.e., benzo(b)fluoranthene and benzo(a)pyrene, was noted.
Both the di verse con cen tra tions of PAHs in crude oils of the Pol ish Low lands, the Carpathians and the Carpathian Foredeep de pos its and the rel a tively small di ver sity in the con tent of perylene may in di cate a rel a tively small in flu ence of geo chem i - cal and bio chem i cal pro cesses tak ing place dur ing bio mass de - cay and sub se quent hy dro car bon mi gra tion in rock for ma tions, but rather pri mar ily an in flu ence of orig i nal or ganic mat ter com po si tion.
A char ac ter is tic high share of 3-cyclic ar o matic hy dro car - bons, es pe cially phenanthrene and fluorene in crude oils, may be use ful for iden ti fy ing en vi ron men tal pol lu tion sources by oil-derived prod ucts. In re cent soils and aque ous sed i ments 4-, 5- and 6-cyclic com pounds, es pe cially fluoranthene, are prev a - lent (Bojakowska et al., 1999). Thus an in crease in the pro por - tion of 3-cyclic ar o matic hy dro car bons in en vi ron men tal sam ples and an in crease in the con tent of phenanthrene and fluorene ver sus fluoranthene may in di cate pol lu tion of the en - vi ron ment by oil-derived prod ucts.
The stud ies were fi nanced by the Com mit tee for Sci en tific Research.
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