Pergamon

Environment International,Vol.25, No. 1, pp. 117-129, 1999 Copyright 1999Eiseviex Science Ltd Printed in the USA.All rightsreu~rved

0160-4120/99IS-seefrontmattex

PII S0160-4120(98)00093-2

CHEMICAL COMPOSITION OF THE WATERSOLUBLE FRACTION OF THE LEADED GASOLINES IN SEAWATER

Talat Saeed and Maha AI-Mutairi
Environmental Sciences Department, Environmental and Earth Sciences Division, Kuwait Institute for Scientific Research, P.O. Box 24885, Safat-13109, Kuwait e-mail: tsaeed@safat.kisr.edu.kw

E19804-139 M (Received 17 April 1998; accepted 28 September 1998)

The chemical composition of the water-soluble fraction (WSF) of gasoline and high-octane gasoline (both leaded) in seawater was investigated. Volatile compounds present were analyzed by purge and trap/gas chromatography (P&T/GC), and confirmed by GC/MS. Polycyclic aromatic hydrocarbons (PAHs) were determined by analyzing the concentrated extract of WSF by single-ion monitoring. A total of 46 volatile compounds were identified in the WSF of gasoline, amounting to about 67 rag/L, while the WSF of high-octane gasoline consisted of 35 volatile compounds which added up to about 77 mg/L. Aromatic compounds were predominant and benzene, toluene, ethylbenzene, and xylenes (BTEX) formed the bulk of the total dissolved components. The concentration of PAHs was higher in the WSF of gasoline (1.3 mg/L) as compared to the PAHs in the WSF of high-octane gasoline (about 1 mg/L). Naphthalene and methylated naphthalenes were the major components in the PAH fraction. The effect of temperature and mixing time on the composition of the WSF was also investigated. 1999ElsevierScienceLtd

INTRODUCTION

Gasoline is one of the most commonly used fuels for outboard motors in many recreational boats and jetskis. Compared with other types of internal combustion engines, outboard motors are inefficient, releasing significant amounts of raw fuel mixtures and fumes into the water (Montz et al. 1982). Hoffman et al. (1984) reported that petroleum-related polycyclic aromatic hydrocarbons (PAHs) make significant contribution to the marine ecosystem through urban storm-runoffs. It was estimated that 71% of the higher molecular weight PAHs and 36% of total PAHs in the Narragansett Bay (Rhode Island) entered as urban runoff. Dumping of untreated sewage also increases the gasoline-related hydrocarbons input into the Gulf. Petroleum-related hydrocarbons in urban runoff have been estimated at about lg/d'person (NRC 1985).
117

Petroleum oil (crude oil and refined petroleum products) spilled in the marine environment undergoes many diverse processes (evaporation, dissolution, photolysis, oxidation, adsorption on to particles, sedimentation, biodegradation, and uptake by biota) which collectively determine the fate of the oil and its impact on the environment. However, the dissolution is of special importance and significance especially from a toxicity point of view. The amount ofoil that dissolves in water is generally small (less than 1%). It is this fraction that contacts and impacts the marine organisms and is, therefore, an important determinant of the oil toxicity. Studies have indicated that the water-soluble fraction (WSF) of petroleum oils is a complex mixture ranging from pentane to PAHs, phenols, and nitrogen- and

118

T. Saeed and M. A1-Mutairi

sulfur-containing heterocyclic compounds (Anderson et al. 1974; Mackay and Shiu 1976). The composition of the WSF depended on the composition of the oil, temperature, and water salinity and on the ratio of the volumes of water and oil that are brought into contact (Shiu et al. 1988). The toxicity of WSF to marine organisms was primarily due to the compounds that dissolved from the oil into the aqueous phase. Benzene and its methylated derivatives are the main class of hydrocarbons found in WSF. Carls and Rice (1990) reported that total mononuclear aromatics constitute about 89% of the total WSF of crude oil. Benzene, toluene, ethylbenzene, and xylenes (BTEX) represented 87.6% of the WSF. The composition of the WSF of gasoline has been the subject of several studies. Coleman et al. (1984) reported the composition of the major components in the WSF of gasoline prepared in drinking water. Murray et al. (1984) described the composition of the WSF of regular gasoline in distilled water in some detail. Shiu et al. (1990) also reported the composition of the major components of the WSF of gasoline. The WSF of summer gasoline in distilled water contained 98 mg/L of compounds. The concentrations of benzene, toluene, and C2-benzene were 30.7, 34.8, and 10.8 mg/L, respectively. Detailed composition of WSF was not reported. Murray et al. (1984) noted that the total dissolved compounds in the WSF of gasoline, also in distilled water, amounted to 156 mg/L. More importantly, the concentrations of benzene, toluene, and C2-benzene were 71 mg/L, 74 mg/L, and 16 mg/L, respectively. Anderson et al. (1974) pointed out that all oils bearing the same name do not necessarily have identical chemical composition. The actual composition of the petroleum product is dependent upon the raw source (crude oil, oil shale, coal, etc.), the degree of chemical modification (for example, cracking), and the physical separation method employed (Coleman et al. 1984). It can, therefore, be reasonably expected that refined petroleum products produced from diverse crude oils may produce different composition of the petroleum product. Secondly, the temperature and the salinity used in the preparation of WSF in the abovementioned studies did not reflect the actual values in the northern Gulf. The pollution due to crude oil, and specifically due to Kuwait crude oil, has been studied in some detail, mostly by measuringthe relatively non-volatile (e.g., PAHs) components of the oil. However, the results of a recent study (Khordagui et al. 1995) indicated that

there are significant and appreciable levels of hydrocarbons related to volatile petroleum products present in the coastal areas of Kuwait and presumably also in other countries of the region. So far there has been no attempt to relate the volatile hydrocarbons in the marine environment to any specific source or parent oil. However, minor spills from small boats were suspected. In literature, extensive information is available about the composition of the WSF of crude oils. However, information about the composition of the WSF of refined products is scarce and fragmented. Gasolines are not chemically well defined and their composition is variable according to the crude oil, refining parameters, and blending. The final product is blended with a view to suit the availability of the constituent fractions, season, and specific requirements of the endusers. The objective of the present study was to investigate the detailed chemical composition of the WSF of gasolines produced locally and under the local conditions (temperatures and salinity) and assess the changes in the chemical composition of the WSF due to different mixing times and seasonal temperatures of the seawater. The composition of the WSF of gasoline and 98-octane (premium) gasoline was investigated in detail.
MATERIALS AND METHODS

Authentic samples of gasoline and 98-octane gasoline (both leaded) were obtained from a retail outlet of the Kuwait National Petroleum Company (KNPC). The samples were kept in an airtight container and stored in a freezer at -20C. The seawater used in the preparation was from an offshore intake well. The water was passed through a series of filters to remove any biota and particulate matter and tested for the presence of any organic compounds. The water was also checked for the presence of any volatile organic compounds. Preparation of WSF The setup used for the preparation of WSF was that proposed by Ali et al. (1995). Figure 1 shows the schematic representation of the setup. It consisted of a 2-L bottle that was kept in a water bath. The temperature of the bath was controlled by circulating water from a water-chiller/heater circulator and was monitored by a thermometer. The circulator controlled the set temperature to +0.1C. The water level in the bath was adjusted so that water and oil layers in the bottle were

WSF composition of leaded gasoline in seawater

I 19

Water Bath r

Nitrogen J q Delivery Tube I

[ Water out ]4 1Oil Samplel Seawater i Stirrer ] ~lectin Bttle I

Magnetic Stirrer

"-1 ir jf Iw.=i. I
Fig. 1. Schematics of the setup used for the preparation of WSF.

below the water level of the bath. The bath was placed on a magnetic stirrer. A Teflon-coated stirring bar (2 cm long) was placed in the bottle. The stirring speed was adjusted so as not to form a large vortex. The oil sample was introduced slowly on top of the water layer through a glass tube with the help of a syringe. The headspace was purged with nitrogen through another tube to expel air. The WSF sample was collected by applying a slight nitrogen pressure that caused the WSF to rise in a glass delivery tube. The stirring was continued for 24 h after which the WSF was removed immediately for analysis or extraction. Preparation of concentrated extract for GC/MS analysis
About 1.5 L of the WSF was taken in a separatory funnel and extracted three times with 10 mL portions of 3:7 mixture of hexane:dichloromethane. The combined extracts were dried over anhydrous sodium sulfate, filtered, and concentrated on a rotary evaporator to about 5 mL and then under a stream of nitrogen to dryness. The residue was taken up in 500 ~tL of methylene chloride.

Purge and trap-gas chromatographic (P&T/GC) analysis The volatile compounds in the WSF were analyzed by P&T/GC using a flame ionization detector. Varian3600 GC was linked to a Tekmar-3000 Purge and Trap Concentrator. A Tekmar cryofocusing module was employed to refocus the volatile desorbed from the trap. Data was acquired and reprocessed by Varian Star Chromatography Software. A 3-mL sample of the WSF was introduced into the purging vessel with a Luer-lock syringe. A preset method, equivalent to U.S. EPA Method-502 (1986), was used for purging and trapping the volatiles. Briefly, the sample was purged for 11 min with helium. The purged volatile compounds were trapped on a Tenax trap. The trap was heated to 225 C to desorb and kept at the same temperature for 2 min during desorption. The desorbed compounds were refocused at the head of an analytical column at -150C after which the capillary interface was heated to 180C and the compounds introduced into the GC. The conditions for GC analysis were as follows: Fused silica capillary column, coated with SPB-624 (Supleco), 1.4 lam film thickness, 30 m long, and

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T. Saeed and M. AI-Mutairi

0.25 mm internal diameter. Helium was used as the carrier gas at 2 mL/min. Initial column temperature was 40C, maintained for 5 min and then programmed to 220C at 4/min. The final temperature was held for 10 min. A flame ionization detector was used for detection. An external standard method was employed for quantitation.

ing the coastal waters. Using NRC (1985) estimates, the urban runoff from Kuwait totals about 730000 kg/y for the population of about 2 million. Table 2 shows the general composition of the two gasolines sold in Kuwait and used in the study. There were significant differences in the naphthene and aromatic contents of these products. Both of the samples contained relatively higher amounts of aromatic compounds.

P& T/GC/MS analysis

The identities of the peaks were ascertained by linking P&T/GC with mass spectrometer. The Tekmar-3000 purge and trap concentrator was linked to the Shimadzu GC-14A through a Tekmar cryofocusing module. The GC was coupled with a Shimadzu QP-2000 quadruple mass spectrometer. The conditions used for GC analysis were the same as given for P&T/GC. The mass spectra of unknown peaks were compared with those standards as well as with the EPA/NIH mass spectral database.

Composition of volatile organic compounds in WSF of regular gasoline

Gasoline is a volatile product and contains mostly aliphatic and aromatic hydrocarbons. It is especially rich in benzene and its derivatives. The composition of the WSF prepared at three different temperatures is presented in Table 3. A total of 46 compounds was identified in the WSF of this product. The WSF of gasoline contained a wide range of volatile compounds (from cyclohexane to methyl indanes). The complexity of the WSF is a reflection of the wide variety of compounds present in gasoline. However, unlike the parent oil, WSF was dominated by the monoaromatics, i.e., benzene and its derivatives. This was to be expected as the solubilities of these compounds were relatively high compared to aliphatic compounds (present in gasoline in higher concentrations). Figure 2 shows the P&T/GC profile of the volatiles present in the WSF of gasoline. Benzene and its derivatives were dominant in terms of quantity (94 to 97%) and the variety of compounds. Aliphatic compounds (n-alkanes and their isomers) were present only as traces (less than 0.5%). Naphthenes (mostly cyclopentane and cyclohexane derivatives) were present in significant amounts (up to about 4.95%). Small amounts of methylphenol and thiophane homologs were also detected. Among the aromatics, BTEX comprised about 98%. A large number of isomers of C3-benzene and C4-benzene were present. As the number of isomers of these compounds was large and many of these isomers had similar mass spectra, many of these were identified as a group (C3-benzene and C4-benzene). In addition to benzene derivatives, other aromatic compounds were also identified. These included indanes (aromatic ring fused with nonaromatic ring). Some compounds containing hetero-atom (other than carbon and hydrogen) were also present in the WSF, though in trace amounts. These compounds have not been reported in the WSF of gasolines before.

GC/MS analysis of PAHs

PAHs in the WSF were determined by the analysis of the concentrated extract of WSF on GC/MS in single ion monitoring (SIM) mode. The instrument used for the analysis was Shimadzu GC-14A/QP-2000 with a split/splitless injector used in splitless mode. The GC conditions were: Fused silica capillary column, coated with SPB-5, 25 m long, and 0.25 internal diameter. The initial temperature was 100C, held for 5 min and then programmed to 280C at 6C. The final temperature was held for 20 min. The ions monitored are given in Table 1. An external standard method was used for quantitation of PAHs. A commercially-available mixture of PAHs (M-610, Supleco) was diluted after the addition of standard solutions of methylated PAHs. The response factors of the available methylated PAHs were used for the isomers for which the standards were not available. The response factor of 1-methyl naphthalene, for example, was used for the calculations of all of methyl naphthalene isomers.
RESULTS AND DISCUSSION

Gasoline is one of the common pollutants in the marine environment, especially in the coastal waters in the vicinity of urban centers. There are many routes through which it reaches the marine environment. One of the most common is the small spill from recreation and water-sports activities. Urban runoff is also responsible for a considerable amount of gasoline reach-

WSF composition of leaded gasoline in seawater

121

Table 1. PAH and methylated PAHs and their ions monitored in the concentrated extract of the WSF of Kuwait crude oil. No. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 PAH name Naphthalene Methyl naphthalene Dimethyl naphthalene Acenaphthylene Acenaphthene Trimethyl naphthalene Fluorene Methyl fluorene Phenanthrene Anthracene Methyl phenanthrene Dimethyl phenanthrene Fluoranthene Pyrene Dimethyl anthracene Benzo(a)anthracene Chrysene Benzo(b)fluoranthene Benzo(k)fluoranthene Benzo(a)pyrene Dibenzoanthracene Indeno(1,2,3)pyrene Benzo(ghi)perylene Abbreviation Naph MNaph DMNaph Acyn Acen TMNaph Fluo MFlou Phen Anth MPhen DMPhen Flan Pyr DMAnth BAnth Chry BbFlan BkFlan Bap DbAnth Indpy Bpery Ion monitored 128 142 156 152 154 170 166 ! 80 178 178 192 206 202 202 206 228 228 252 252 252 278 276 276

Table 2. Composition (g/100 g) of gasoline and high-octane gasoline used for the preparation of WSF. Gasoline Carbon no. C5C 6-

High-octane gasoline Aromatics 0.00 2.00 21.78 8.54 4.13 0.94 37.4 Olefins 0.19 3.79 2.64 0.66 0.24 0.00 7.44 Paraffins 14.25 10.91 10.07 4.75 0.15 0.3 41.27 Naphthenes 0.23 1.51 4.14 !.97 1.69 0.00 9.54 Aromatics 0.00 2.21 24.83 9.31 4.29 1.04 41.69 Olefins 0.06 3.67 2.34 0.55 0.05 0.00 6.71

Paraffins 9.87 12.73 11.0 5.59 0.27 0.04 42.32

Naphthenes 0.41 2.62 5.12 2.48 1.67 0.00 12.3

C7C8C9C19Total

Comparing these results with those reported in literature, it was apparent that the present results were not in complete agreement. One reason for the difference was the use o f distilled water in the preparation of WSF in the abovementioned studies which resulted in higher levels. Secondly, the composition of gasoline itself was variable. Lastly, the method of preparation o f WSF has not been standardized and variable methods o f WSF preparation produced different levels of vo-

latiles in the WSF. Montz et al. (1982) described detailed composition of the WSF produced by the outboard motors. C2- and C3-benzenes were the dominant compounds. The total concentration of the soluble compounds, after 2 h of stirring, ranged from 11.5 to 17.7 mg/L, which increased to 67 mg/L after 24 h of stirring. The group summary of these findings is presented in Table 4. The composition of the aromatics is also

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Table 3. Composition of WSF of gasoline (90-octane, leaded) in seawater (Ixg/L). 15C 4h 112 153 3 8133 16 7 102 47 15 31 8059 10 7 41 36 8 592 1939 9 0 902 11 34 169 52 58 70 249 3 2 2 67 79 4 6 4 22 1 2 5 5 11 9 1 2 3 21 092 25C 4h 339 777 0 9648 12 25 24 72 9 7 9569 5 8 50 43 9 700 2312 4 0 1088 12 41 213 54 69 86 305 4 2 2 83 100 4 8 4 28 1 3 6 7 14 11 2 2 3 25 762 35C 4h 496 1028 0 11 670 11 18 110 80 0 20 12 522 15 8 77 52 39 984 3232 9 0 1571 19 61 300 86 100 125 435 6 3 2 115 146 4 8 2 35 1 3 6 7 14 13 1 1 2 33 435

Peak 1 2 3 4 5 6 7 8 9 10 11 12 13 14 14a 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45

Name Methyicyelopentane Cyclohexane 3-Methylhexane Benzene n-Heptane Methylcyelohexane Octane isomer 1,3-Dimethylcyelopentane Octane isomer Dimethyleyclohexane Toluene n-Octane Dimethyleyciohexane Ethylmethylcyclohexane Methylphenol Methylthiophane Ethylbenzene p- & m-Xylenes Dimethylthiophane Dimethylthiophane o-Xylene Cumene n-Propylbenzene C3-Benzene isomer C3-Benzene isomer Mesitylene C3-Benzene isomer C3-Benzene isomer 2-Methylpropylbenzene p-Cymene m-Cymene C3-Benzene isomer Indane C4-Benzene isomer 3-Methylpropylbenzene C4-Benzene isomer o-Cymene 1,2 Diethylbenzene 1,4-Diethylbenzene C4-Benzene isomer Ethyldimethylbenzene C4-Benzene isomer l-Methyl indane C4-Benzene isomer 2-Methyl indane 4-Methyl indane Total

2h 70 59 1 4475 9 17 22 5 3 10 4420 10 4 23 19 4 332 1084 17 0 503 8 22 95 31 35 40 142 2 1 4 38 45 2 4 2 16 0 1 3 3 7 5 1 2 2 11 595

24h 952 1286 0 23 177 65 15 48 151 38 69 19 014 11 22 112 93 28 1840 6004 9 3 2665 28 72 411 0 77 93 246 2 1 1 31 50 1 2 1 9 0 1 1 3 0 2 0 0 1 56 634

2h 40 94 19 5642 22 32 39 32 7 7 5550 7 6 27 21 5 412 1354 6 0 639 8 26 121 40 43 53 192 2 1 1 54 64 3 5 3 17 1 2 4 5 10 8 1 2 3 14 632

24h 903 1285 0 24 546 70 28 33 126 9 3 27 225 32 20 116 102 27 2042 6638 6 2 2863 27 66 274 82 58 71 196 2 1 0 26 43 1 2 1 9 0 0 1 1 3 2 0 0 1 66 945

2h 300 123 0 6286 31 18 132 51 0 25 6575 8 5 45 23 24 522 1706 16 0 834 10 33 157 48 54 68 239 3 1 4 66 79 4 6 3 26 1 2 6 5 12 9 2 3 5 17 569

24h 895 1614 0 23 789 53 35 163 247 0 4 28 016 13 18 114 97 27 2082 6422 6 0 2526 17 40 154 51 31 39 127 1 0 0 20 36 1 2 8 1 1 0 0 0 3 2 0 0 0 66 656

WSF composition of leaded gasoline in seawater

123

17

It

20

36 16

~o/
~ $5 3

41

\11 $4.

./42

44

145
~5 24
,4

14a

i
S S

1_

23 22 I|

l;'lt'
SO
I I I I

2 x
. . . .

Fig. 2. GC chromatograrn of the WSF of regular gasoline (see Table 3 for peak identification).

shown in this table. Benzene and toluene together made up about 80% of the total aromatics and C2-benzenes (ethylbenzene and xylenes) comprised about 18% of the aromatics in the WSF of gasoline. Eight isomers of C3-benzene were detected but the total contribution of all of these isomers amounted to about 1% of the total aromatics after 24 h of stirring. On the other hand, 13 isomers of C4-benzene comprised about 0.1% of the total.

Effect of stirrfng time The effect of stirring time on the composition of individual components as well as on the total is presented in Table 3. The effect of stirring time of the different groups and subgroups is summarized in Table 4. The concentration of WSF increased greatly with time. The concentration increased by about 80% between 2 h and 4 h. After stirring gasoline with sea-

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T. Saeedand M. A1-Mutairi

Table 4. Group summaryof the WSF of gasoline (90-octane, leaded). 15C Group name 2h 4h 24 h 2h 25C 4h 24 h 2h 35C 4h 24 h

Total aliphatics (lag/L) 24 17 26 56 43 130 57 44 101 Total naphthenes(lag/L) 192 462 2570 245 647 2486 822 1819 3055 Total aromatics(lag/L) 11 323 20 495 53 730 14 266 24 373 64 180 16 769 31 473 63 370 Total others (lag/L) 40 53 130 32 55 136 62 100 130 Aliphatics % 0.21 0.08 0.05 0.39 0.17 0.19 0.32 0.13 0.15 Naphthenes % 1.66 2.20 4.55 1.68 2.57 3.71 4.64 5.44 4.58 Aromatics % 97.78 9 7 . 4 7 95.17 97.72 9 7 . 0 3 95.89 94.69 9 4 . 1 3 95.07 Others % 0.35 0.25 0.23 0.22 0.22 0.20 0.35 0.30 0.2 Benzene % 39.52 3 9 . 6 8 43.14 39.55 3 9 . 5 8 38.25 37.49 3 7 . 0 8 37.54 Toluene % 39.04 3 9 . 3 2 35.39 38.91 39.26 42.42 39.21 3 9 . 7 9 44.21 C2-Benzene % 16.95 16.75 19.56 16.86 16.82 17.99 18.26 18.39 17.24 C3-Benzene % 3.28 3.14 1.72 3.38 3.21 1.21 3.63 3.58 0.73 Ca-Benzene % 0.41 0.32 0.03 0.38 0.31 0.03 0.45 0.29 0.03 Others % 0.81 0.79 0.16 0.92 0.82 0.11 0.96 0.88 0.09

water for 24 h, the total amount of soluble components increased by about 450% compared with the 2-h sample. The different groups were not affected uniformly. Aliphatics, aromatics, and hetero-atom containing compounds decreased proportionally, while naphthenes increased their share with time. Among the aromatics, different subgroups behaved differently. The percentage o f benzene, for example, increased slightly with time at 15 C, whereas it remained more or less steady at 25C and 35C. Toluene, on the other hand, decreased slightly with time at a temperature of 15C, and increased at 25C and 35C. The percentage of C2-benzenes increased at lower temperatures (15C and 25 C) with increasing stirring time, while at higher temperature (35C), it remained steady or decreased slightly. The share of C3- and Ca-benzene in the total decreased sharply with stirring time at all three temperatures.

Effect of temperature
The effect of temperature on the composition of the WSF of gasoline was as expected, i.e., with increase in temperature, the levels of organic compounds increased. The increase was significant in the early hours of the dissolution process. For example, there was an increase o f about 25% with every rise of 10C in the temperature o f the water in the first 4 h. However, after 24 h o f stirring, the increasing temperature did not have the same effect. The increase in the level of total volatile organic compounds from 15 C to 25 C was only

18% and no appreciable increase was observed between 25C and 35C in the samples collected after 24 h of stirring. The effect of the increase in the temperature on the relative concentration of different groups varied. In the case of aliphatics, the percent concentration increased between 15C and 25C and decreased when the temperature increased to 35C. Naphthenes, on the other hand, increased with increasing temperature. The percentage of aromatics in the total WSF, generally, decreased when the temperature was increased from 25C to 35C. Individually, in 24-h samples, the increasing temperature had a different effect on different compounds. The concentration of benzene was not affected significantly by increasing temperature. On the other hand, the concentration of toluene increased appreciably when the temperature was increased from 15 C to 25C, while only a slight increase was observed when the temperature was increase further. A similar trend was observed for ethylbenzene, p- and m- and o-xylenes. The concentrations of C3- and Ca-benzenes decreased appreciably with increasing temperature.

Volatile organic compounds in the WSF of high-octane gasoline (98-octane, leaded)

Like gasoline, the high-octane version is volatile as it contains mostly low molecular weight compounds (C6-C10). In literature, there is relatively little information about the composition of the WSF of high-octane

WSF composition of leaded gasoline in seawater

125

17 4 11 16 20

27 24 1 3 78 9 56 10 22 ~ 31 14 23 /26

Fig. 3. GC chromatogramof the WSF of premium gasoline (see Table 5 for peak identification).

gasoline in seawater. High-octane gasoline produced in Kuwait contained a higher proportion of aromatic compounds, especially benzene and toluene. Figure 3 shows the chromatogram of gasoline and high-octane gasolines under identical conditions. A visual comparison shows the important quantitative differences in the composition of these products. High-octane gasoline contained appreciably higher amounts of benzene, tolu-

ene, and C2-benzenes. However, levels of C4-benzenes were considerably less than in regular gasoline. This indicated that the composition of the WSF of this product would be different from that of gasoline in this respect. Table 5 presents the detailed composition of the WSF of high-octane gasoline at different temperatures and at different stirring times. A total of 35 volatile compounds were identified.

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T. Saeed and M. AI-Mutairi

Table 5. Composition of WSF of high-octane gasoline (98-octane, leaded) in seawater (lag/L). 15C Peak 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 Name Methylcyclopentane Cyclohexane 3-Methylhexane Benzene n-Heptane Methylcyclohexane Octane isomer 1,3-Dimethylcyclopentane Octane isomer Dimethylcyclohexane Toluene n-Octane Dimethylcyclohexane Ethylmethylcyclohexane Methylphenol Methylthiophane Ethylbenzene p- & m-Xylenes o-Xylene Cumene n-Propylbenzene C3-Benzene isomer C3-Benzene isomer Mesitylene C3-Benzene isomer C3-Benzene isomer C3-Benzene isomer Indane CcBenzene isomer 3 -Methylpropylbenzene C4-Benzene isomer o-Cymene C4-Benzene isomer Ethyldimethyibenzene C4-Benzene isomer Total 2h 26 208 5 5638 3 10 14 3 0 2 6273 2 2 14 40 2 440 1419 622 7 17 75 27 24 30 102 21 11 0 0 0 0 0 0 0 15 038 4h 39 267 1 11 417 3 9 50 4 0 9 12 821 6 5 32 78 5 885 2864 1246 15 34 150 53 48 64 200 43 20 1 0 2 0 0 0 0 30 372 24h 232 1044 44 30 452 6 23 175 29 0 0 35 834 14 9 55 145 6 1033 2902 1003 5 13 40 35 16 15 51 8 5 0 0 0 0 0 0 0 73 191 2h 28 271 0 7716 11 12 21 0 1 0 8714 4 3 24 58 3 625 2038 914 12 27 118 44 40 52 169 37 17 1 0 2 0 0 0 1 20 963 25C 4h 38 287 0 12 854 10 12 52 0 2 9 14 584 8 5 36 92 5 1021 3330 1474 18 42 188 63 61 80 253 56 25 1 1 2 0 0 0 1 34 610 24h 423 1155 0 31 790 5 17 52 0 0 0 35 628 13 7 47 136 5 945 2729 777 5 12 36 32 15 13 46 6 3 0 0 0 0 0 0 0 73 897 2h 48 296 0 10 811 18 23 53 0 5 0 12 363 6 4 32 81 3 880 2874 1284 16 39 169 61 57 75 240 54 24 1 2 1 4 1 1 2 29 527 35C 4h 49 550 0 17 328 12 13 79 0 11 0 20 217 11 6 30 130 3 1417 1838 2053 24 55 242 77 75 98 288 50 25 0 0 0 0 0 0 0 44 680 24h 677 947 0 32 412 6 18 113 0 30 0 37 368 14 7 35 143 4 1010 2908 877 6 16 54 37 17 20 65 11 7 0 0 0 0 0 0 0 76 802

T h e c o n c e n t r a t i o n o f t o t a l s o l u b l e c o m p o u n d s in t h e WSF of high-octane gasoline was significantly higher than the WSF of regular gasoline. The concentration r a n g e d f r o m 15 m g / L t o a b o u t 30 m g / L a f t e r 2 h o f s t i r r i n g c o m p a r e d w i t h 11.5 to 17.5 m g / L in t h e W S F o f g a s o l i n e . T h e t o t a l c o n c e n t r a t i o n a f t e r 24 h o f stirr i n g i n c r e a s e d t o 7 3 - 7 6 m g / L ( 5 6 t o 66 m g / L in c a s e o f

g a s o l i n e ) . B e n z e n e a n d its d e r i v a t i v e s w e r e p r e d o m i n a n t ( T a b l e 6). A l i p h a t i c s a n d h e t e r o - a t o m - c o n t a i n i n g c o m p o u n d s w e r e p r e s e n t o n l y in t r a c e s . T h e t o t a l c o n centration of naphthenes was also low, but not insignificant. Among the aromatic subgroups, benzene and toluene accounted for between 90 and 93% of the total aromatics.

WSF composition of leaded gasoline in seawater

127

Table 6. Group summary of the WSF of high-octane gasoline. 15C Group name 2h 4h 24 h 2h 25C 4h 24 h 2h 35C 4h 24 h

Total aliphatics (lag/L) 25 29 44 28 32 35 51 Total naphthenes (~g/L) 268 397 1544 347 427 1684 432 Total aromatics (Ixg/L) 14 706 29 863 71 410 20 527 34 054 72 038 28 959 43 Total others (~tg/L) 41 83 152 61 98 140 84 Aliphatics % 0.17 0.09 0.06 0.13 0.09 0.05 0.17 Naphthenes % 1.78 1.31 2.11 1.65 1.23 2.28 1.46 Aromatics % 97.78 98.32 97.62 97.92 98.39 97.48 98.08 Others % 0.27 0.27 0.21 0.29 0.28 0.19 0,29 Benzene % 38.34 38.23 42.64 37.59 37.74 44.13 37,33 Toluene % 42.65 42.93 50.18 42.45 42.83 49.46 42,69 C2-Benzene % 16.87 16.73 6.92 17.42 17.11 6.18 17,40 C3-Benzene % 2.06 2.03 0.25 2.43 2.23 0.23 2.46 Ci-Benzene % 0.00 0.01 0.00 0.02 0.01 0.00 0.04

46 68 7!5 1780 787 74 806 133 147 0.10 0.09 1.60 2.32 98.00 97.40 0.30 0.19 39.57 43.33 46.17 49.95 12.12 6.41 2.08 0.30 0.00 0.00

Individually, the concentrations of benzene and toluene were significantly higher than in the WSF of gasoline. In the WSF of high-octane gasoline, the benzene concentration was about 31 mg/L while in gasoline it did not exceed about 24 mg/L. Similarly, in case of toluene, in the WSF of high-octane gasoline, the levels reached were 37 mg/L after 24 h of stirring, while in the WSF of gasoline, it reached only 28 mg/L. On the other hand, the concentration of C2-benzenes in the WSF of premium gasolines was dramatically less than found in the WSF of gasoline (about 6% compared with about 18%). Similar observations were made for C 3- and C4-benzene. The sharply lower concentration of C2-benzenes in the WSF was surprising, as the concentration of these compounds in the parent product was more than in the gasoline.
Effect of stirring time

time at 15 C. The effect of increasing time on different groups and subgroups was comparable with the WSF of gasoline (Table 5). Aliphatics and hetero-atomcontaining compounds decreased with time in their percentage contribution to the total. Correspondingly, the percentage share of naphthenes increased with time. Aromatics, as a group, remained more or less unchanged in their percentage contribution to the total. The percent share of benzene and toluene increased considerably with time while that of C2-benzenes and C3-benzenes decreased over the same period.
Effect of temperature

The change in the composition of the WSF after different stirring times is presented in Table 5. As observed in the gasoline sample, the concentration of individual compounds as well as of the groups increased with time. The overall concentration of organic compounds doubled from 2 h stirring time to 4 h at 15C. A five-fold increase was observed when the stirring time was 24 h. The increase in the overall concentration of the WSF was the reflection of increasing levels of major individual compounds. For example, the concentration of benzene and toluene increased about six-fold between 2 h and 24 h stirring

The increase in temperature of the seawater resuited in higher solubilities of the components of premium gasoline. Increasing the temperature by 10C resulted in an increase of about 40% in the total organic compounds dissolving in seawater after the first 2 h of stirring time. However, when the stirring continued for 24 h, the levels of soluble compounds reached about the same value (range 73.1 to 76.8 mg/L). It can be inferred that, at lower temperatures, the dissolution process is slow. After an extended period of time (24 h), the dissolution reaches about the same level at temperatures used in these experiments. It is clear from Table 6 that the effect of temperature was more or less similar on different groups. Even among the different subgroups of aromatics, the percentages of these subgroups did not change significantly.

128

T. Saeed and M. AI-Mutairi

Table 7. Levels of PAHs (~tg/L) in the WSF of gasoline by GC/MS (SIM). No. 1 2 3 4 5 6 7 8 9 10 !1 12 PAH Naphthalene Methyl naphthalene Dimethyl naphthalene Acenaphthene Trimethyl naphthalene Fluorene Methyl fluorene Phenanthrene Anthracene Methyl phenanthrene Dimethyl phenanthrene Pyrene Total PAHs 15C 890.2 223.8 24.9 0.2 58.9 0.6 20.9 1.3 4.0 22.6 8.6 0.0 1255.9 25C 703.7 160.9 23.3 0.2 53.4 0.6 7.7 1.1 1.6 12.6 4.7 0.0 969.7 35C 710.9 162.9 26.0 0.2 44.2 0.5 5.0 0.5 1.2 8.6 2.5 0.1 962.5

Table 8. Levels of PAHs (~tg/L) in the WSF of high-octane gasoline by GC/MS (SIM). No.
1

PAH Naphthalene Methyl naphthalene Dimethyl naphthalene Acenaphthylene Acenaphthene Trimethyl naphthalene Fluorene Methyl fluorene Phenanthrene Anthracene Methyl phenanthrene Dimethyl phenanthrene Fluoranthene Pyrene Total PAHs

15C 581.4 203.2 64.9 0.0 0.4 153.4 1.1 0.6 2.2 2.1 16.6 12.8 0.0 0.1 1038.8

25C 498.0 201.4 46.0 0.3 0.4 103.2 0.8 4.4 2.1 2.3 11.1 7.3 0.0 0.0 877.2

35C 411.0 155.3 25.7 0.0 0.2 16.5 0.7 3.0 1.5 1.2 9.5 4.0 0.1 0.1 628.7

2 3 4 5 6 7 8 9 10 11 12 13 14

PAHs in the WSF of gasoline

Gasoline does not contain significant amounts o f higher molecular weight compounds. The PAHs in the W S F o f gasoline w e r e expected to be different than those in crude oil. Table 7 presents the results o f qualitative and quantitative analysis o f the extract o f the W S F o f gasoline by G C / M S using SIM. Six PAHs and six methylated P A H s were detected. Naphthalene was the single most abundant c o m p o u n d in this fraction and comprised about 70% o f the total. Naphthalene h o m o l o g s were present in appreciable concentration. Naphthalene and its homologs constituted

about 90% o f the total PAHs. Methyl fluorene, methyl phenanthrene, and dimethyl phenanthrene were other PAHs present in appreciable concentrations. The effect o f change in temperature can also be noticed from Table 7. Increasing temperature caused significant decrease in the P A H levels in the WSF. The concentration o f total PAHs decreased from 1256 Ixg/L at 15C to 963 lxg/L at 35C. The total P A H concentration in the WSF o f gasoline was m u c h higher than the levels found in the WSF o f K u w a i t crude oil. This was probably due to the fact that refined products are enriched in a narrow range o f c o m p o u n d s in the refining process.

WSF composition of leaded gasoline in seawater

129

PAHs in the WSF of high-octane gasoline

The composition o f P A H s in the WSF o f this product was qualitatively similar to that o f gasoline as determined by G C / M S . There were, however, important quantitative differences. The total concentration was about 20% less than the W S F o f gasoline. PAHs in the W S F were dominated by naphthalene and it's methylated derivatives (Table 8). In total, 14 PAHs were detected, although mostly in trace amounts. Because o f the volatile nature o f the product, it conmined only up to three-ring P A H s (phenanthrene). The total levels and the overall composition o f PAHs were comparable with gasoline levels (about 1000 ~tg/L). Methyl fluorene levels were, however, considerably lower in the W S F o f high-octane gasoline as compared to the levels in gasoline. The total was, however, considerably lower for the sample prepared at 35 C, probably due to excessive losses during concentration o f the extract (indicated by relatively low levels o f trimethyl naphthalene at 35C). Another possibility is that, at higher temperatures, monoaromatics b e c o m e more soluble and force out less soluble PAHs. In general, the differences in the P A H composition reflected the differences in the composition o f the parent products.

Acknowledgment--The authors wish to gratefully acknowledge the partial funding of these studies provided by the Kuwait Fund for Advancement of Sciences (KFAS). Dr. G. Michael (Petroleum Technology Department, KISR) is thanked for carrying out PIONA analysis of the gasolines.
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