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Survey of polynuclear aromatic compounds in oil refining areas
Environmental Pollution 43 (1987) 195-207
Survey of Polynuclear Aromatic Compounds in Oil Refining Areas D. L. Karlesky, G. Ramelow,* Y. Ueno,'l"I. M. Warner Department of Chemistry, Emory University, Atlanta, Georgia 30322, USA
& Chu-Ngi Ho Department of Chemistry, East Tennessee State University, Johnson City, Tennessee 37614, USA (Received 19 August 1985; revised version received 11 February 1986; accepted 27 May 1986)
ABSTRACT Air samples in and around refinery areas were collected over a 3-year period. The results of the analysis for polynuclear aromatic compounds listed as priority pollutants by the United States Environmental Protection Agency are presented. The particulate matters in the air were collected on glass fiber filters using high volume samplers. These samples were later Soxhlet extracted with cyclohexane, and then extracted with DMSO/pentane for isolation of the polynuclear aromatic compounds. These extracts were then analyzed using gas chromatography-mass spectrometry for specified polynuclear aromatic compounds. It was found that much higher concentrations of these aromatic compounds were found in one refinery compared to another one. In general, the number of these priority pollutants detected and their * Present address: Department of Chemistry, McNeese State University, Lake Charles, Louisiana 70609, USA. t Present address: Tobacco and Health Research Institute, University of Kentucky, Cooper and Alumni Drives, Lexington, Kentucky 40506-0236, USA. 195 Environ. Pollut. 0269-7491/87/$03"50 © Elsevier Applied Science Publishers Ltd, England, 1987. Printed in Great Britain
196
D.L. Karlesky et al. concentrations were higher in sites inside the refineries relative to a site outside the refineries.
INTRODUCTION Growing concern for the quality of our environment has prompted many researchers to study the effect of air pollution on human health. Epidemiological studies have indicated that the incidences of lung cancer are higher in urban than in rural areas (Henderson et al., 1975). The higher incidences are suspected to be due to the greater amount of mutagenic compounds found in particulate matters in urban air (Walker et al., 1982). Other researchers have also shown that there seems to be a relationship between the general location of industrial pollutant sources and geographical distribution of certain types of cancer, such as gastric (MacDonald, 1974), bladder and liver (Hoover & Fraumeni, 1975) and lung (Blot & Fraumeni, 1982). In particular, a study by Blot et al. (1977) found that incidences of skin, nasal and lung cancer were higher among workers in oil refinery areas. Polynuclear aromatic compounds (PNAs) constitute an important class of chemical pollutants associated with many of these industrial areas (Henderson et al., 1975; Schimberg, 1981; Rantanen, 1983). Many of these compounds are on the United States Environmental Protection Agency (EPA) priority pollutant list, a list that comprises compounds which have been found to be ubiquitous environmental pollutants with possible potential health hazards. Many of these PNAs are known or suspected carcinogens and/or mutagens. They may also react with other common air pollutants to produce hazardous compounds (Josephson, 1981). Depending on the source of pollution, environmental mixtures of PNAs can be extremely complex. Well conceived sampling techniques, prudent separation procedures and powerful analytical instrumentation are essential for successful analysis of these environmental samples. Capillary column gas chromatography (GC), capable of very high resolution separation, has been used extensively to analyze PNAs from complex air samples (Dong et al., 1976; Giger & Shaffner, 1978; Radecki et al., 1978). A mass spectrometer (MS) can ideally serve as a detector for the identification of the eluted trace components. In this paper, we present our use of GC-MS to survey for PNAs in air samples collected in and around two oil refineries in east Texas. The area is chosen because it is well known for its large concentration of chemical and petroleum industries which are potential sources of emitters of pollutants. Moreover, this area has been reported (Blot et al., 1977) to have high incidences of cancer among its workers.
Polynuclear aromatic compounds in oil refinin9 areas
197
MATERIALS AND M E T H O D S
Chemical and reagents The PNA standards were obtained from various sources at 95~o purity or better, and were used as received. Cyclohexane and pentane (Burdick and Jackson, Muskegon, MI) and water (J. T. Baker, Phillipsburg, PA) were all H P L C grade. Dimethylsulfoxide (DMSO) (Fisher, Fairlawn, N J) was of reagent grade. All these chemicals were used as received. High purity nitrogen and helium (Pye Barker, Atlanta, GA) were also used as received.
Particle collection All particle collection was accomplished using a Sierra model 305-2000H high volume air sampler (Sierra Instruments, Carmel Valley, CA) with a constant flow controller. All samples were collected using a flow rate of 40 ft a m i n - ~ (cfm). The air sampler was fitted with glass fiber filters which can collect particles greater than 0.3 # with better than 9 9 ~ efficiency. A record of air volume was provided and a timer registered the total elapsed time. A Sierra model 235 five stage, high volume cascade impactor was used with the air sampler to measure the complete particle size distribution from 0"5-10 #. The cascade filters (No. C-230-CF) were made of paper and supplied by Sierra Instruments.
Instrumentation for analysis Gas chromatography was performed on a Hewlett Packard 5880 gas chromatograph (Avondale, PA) with a flame ionization detector (FID). A 30-m, DB-5, SE-54 coated fused silica capillary column with 0.20 m m inside diameter (J & W Scientific, Sunnyvale, CA) was used for PNA separation. Grob's splitless injector was used for sample injection. The injection port temperature was 250°C and the carrier gas was helium, with a flow rate of 50 cm s-~ at 270°C column temperature. The initial column temperature during injection was 30°C and held for 0"3 min after injection. The temperature was then raised to 270°C at a rate of 8°C m i n A Finnigan model 6000 series G C - M S (Cincinnati, OH) at Emory University was used for parts of the analysis. The same capillary column was used, but with the helium at a column linear flow velocity of 75 cm s- 1 at 270°C. Another G C - M S at Texas A&M University was also used for parts of the analysis. This one was a Hewlett Packard system (Avondale, PA) consisting of model 5710A GC, model 5980A MS and model 5933A data system. We also had our samples analyzed in parallel by Southern
198
D.L. Karleskyet al.
Research Institute (Birmingham, AL) using the same column type and instrument conditions.
Air sampling Three separate air sampling trips were made to the same area of east Texas. The dates were: 16 August 1981, 26 July 1982 and 9 May 1983.
16 August 1981 sampling Samples were collected at two oil refineries: Site A and Site B. At Site A, samples were collected directly on two units. Unit 1 was a vacuum distillation unit where partially refined crude oil was further graded by vacuum distillation. After consultation with the industrial hygienist at the refinery, the sampling apparatus was placed near a p u m p room, where the various grades of oil were pumped to different destinations in the refinery. We were informed that one of the oil grades, No. 2 fuel oil, pumped through this room would probably contain PNAs. One 48-h high volume sample (AI) was collected here. The second unit, Unit 2, sampled at Site A, was a catalytic cracking unit. The sampler was placed almost directly beneath the cracking tower. A 24-h high volume air sample (A2) was collected here. At the other refinery, Site B, samples were collected approximately 100 yards away from a vacuum distillation unit in a relatively open area. Two samples, B 1 and B2, were collected over two consecutive 48-h periods.
26 July 1982 sampling In July 1982, sampling was repeated at the same locations at Site A. Air samples were also taken at Site C, a Texas State Air Control Experimental Station not too far away (within a 5-mile radius) outside the refineries. We had 4 days of sampling done using three high volume samplers. One sampler was at Site C collecting four consecutive 24-h samples (C1-C4). At Unit 1 of Site A, one of the air samplers was fitted with a cascade impactor collecting two 48-h samples at the same time. Simultaneously, also at Unit 1, in the vicinity of the cascade impactor, two consecutive 24-h samples (A11, A12) were gathered. On the third day, this air sampler was moved to Unit 2, and two consecutive 24-h samples (A21, A22) were also collected there.
9 May 1983 sampling Sampling was carried out again at Site A. However, due to new safety regulations, sampling directly on the units was not permitted. Therefore, sampling was moved to a location near Unit 1, about 25 yards away from the previous sampling site. Two 24-h samples, AN1 and AN2, were col-
Polynuclear aromatic compounds in oil refining areas
199
lected here. Unit 2 was not in operation during this sampling trip, so two 24-h samples (A31, A32) were taken near another cracking unit (Unit 3) in the refinery. Again, four consecutive 24-h samples (C1-C4) were collected at the same site, Site C, outside the refinery at the Texas State Air Control Experimental Station.
Sample handling Immediately after sample collection, the used filters and cartridges were wrapped in aluminum foil and stored in a freezer until sample preparation and analysis. All the particulate samples on glass fiber and cascade filters were Soxhlet extracted by folding them to fit in the extractor with 300 ml of cyclohexane. The extraction was run for 24 h with the solvent recycling every 15 min, or so. The extracts were concentrated by rotary evaporation to near dryness and then redissolved to 10 ml solutions in cyclohexane. For the samples collected in 1981, half of the final 10ml was further separated using a DMSO/pentane extraction procedure described by Natusch & Tomkins (1978). From this, a final 1 ml solution was submitted for G C - M S analysis at Texas A&M University using the Hewlett Packard system. The other half of the 10ml extract was reduced to i ml and sent to Southern Research Institute for G C - M S analysis using selective ion monitoring (SIM). For the samples collected in 1982, the final volume from the extract was reduced to 0.20 ml and again sent to Southern Research Institute for G C - M S analysis. For those collected in 1983, the final volume of the Soxhlet extract was reduced to 1 ml and analyzed on the Finnigan 6000 G C - M S without using SIM.
Chromatographictechniques A chromatogram of a standard solution of priority PNA pollutants on the SE-54 coated fused silica capillary column, using F I D detection, is used as a reference for identification of the compounds. The components of the standard solution are listed in Table 1. The oven temperature has been programmed to obtain optimum resolution. Although not shown here, the resolution was good even for several isomers, or c o m p o u n d pairs, which are difficult to resolve; for example, phenanthrene and anthracene, benzo(b)fluoranthene and benzo(k)fluoranthene. The 1981 samples were partly analyzed on the Texas A & M University Hewlett Packard G C - M S using the same fused silica column as on our GC. When a GC total ion chromatogram of 2 pl of Soxhlet extract of the PNAs standard solution was obtained, the peak shape and the resolution of the
D. L. Karlesky et al.
200
TABLE 1 Standard PNA Solution and Its Components Abbreviations used in this manuscript
Full name
1. Naph 2. Acyn 3. Acen 4. Flor 5. Phen 6. Anth 7. Flur 8. Pyre 9. 1 , 2 - B A 10. Chry 11. B ( b ) F 12. B(k)F 13. B ( a ) P 14. Pery 15. IPyr 16. DBA 17. B ( g , h , i ) P
Naphthalene Acenaphthylene Acenaphthene Fluorene Phenanthrene Anthracene Fluoranthrene Pyrene 1,2-Benzanthracene Chrysene Benzo(b)fluoranthene Benzo(k)fluoranthene Benzo(a)pyrene Perylene Indeno(1,2,3,-c,d)pyrene 1,2,5,6-Dibenzanthracene Benzo(g,h,i)perylene
higher molecular weight compounds were poorer than using FID. To improve the selectivity and sensitivity, SIM was applied, and all the components were then resolved and detected. The ions monitored at different time intervals are tabulated in Table 2. The value of the technique was more evident when an air sample was analyzed. For a G C / F I D chromatogram of an air sample which had been Soxhlet extracted, although one could try to match the retention times of peaks of the chromatogram with that of the P N A standard solution, it was difficult to obtain quantitative measurements. The same difficulty was encountered when a GC total ion c h r o m a t o g r a m of the same air sample was taken. The poor resolution would not permit one to obtain any reliable qualitative identification and quantitative results. However, when we acquired the SIM chromatogram of the same sample under identical chromatographic conditions, we could detect all of the seventeen PNAs due to greater selectivity and sensitivity of the technique. These procedures and parameters were used in all subsequent analyses.
Filters and quantitative analysis A number of workers have investigated the use of filters for particulate sampling. Schwartz and co-workers (1981) conducted a study which sug-
Polynuclear aromatic compounds in oil refining areas
201
TABLE 2 Mass to Charge Ratios Monitored for Analysis of Priority PNA Pollutants Time interval
role
Compound
1-13 min
128 152 154 166
Naph Acen Acyn Flor
14~26 min
166 178 202 222
Phen, Anth Pyre 1,2-BA Chry
27-38.5 min
202 228 252
Flur, Pyre Chry, 1,2-BA B(b)F, B(k)F, B(a)P, Pery
39-end
252
B(b)F, B(b)F, B(a)P, Pery
276 278
IPyr, B(g,h,i)P DBA
gested that loss of analytes could occur if glass filters were used for sampling over an extended period (24-h and more). Lee et al. (1980) carried out comprehensive studies of particulate sampling using different types of filters. They found that recoveries of the same PNA, benzo(a)pyrene were quite different on those filters. They found that filters with Teflon binders; for example, polytetrafluoroethylene (PTFE) filters, had better recoveries than the glass filters. They proposed that the surface properties of the glass filters leading to catalysis, affinity and uptake of moisture and reactivity, could account for loss, degradation and transformation of the analytes. However, they found that the PTFE Teflon filters unfortunately contained more fluorescent background impurities in their extracts. Therefore, it is extremely difficult to be able to be rid of any spurious effects and to reproducibly account for losses and efficiencies. From our experience, we agree with these remarks. Therefore, we do not account for losses and efficiencies. This is consistent with our goal of providing a general survey of the PNA content in oil refining localities.
RESULTS A N D DISCUSSION The apparent total concentration, in ng 100 m-3 air, of each PNA on the priority pollutant list found on the filters collected in 1981, after Soxhlet
D. L. Karlesky e t al.
202
TABLE 3 Concentration Pentane
of PNAs
Found
on Air Filters After Soxhlet and DMSO/
Extraction. Collected August
1981 (in ng 100 m-3 Air)
Site A
Compound Naph
Unit 1 ,41 .
Site B Unit 2 .42
.
Acyn
.
Unit 1 BI
Unit 2 B2
.
--
--
--
1.8
--
--
373
Flor
11.8
248
Phen
--
913
Acen
85"6 15 2 0 0
79-3 3 360
Anth
--
4.1
343
290
Flur
--
57.7
503
1 020
Pyre
--
356
2 770
1 880
--
--
118 160
1,2-BA
5.1
Chry
--
--
--
B(b)F' 1 B(k)F)
38.9
--
1 400
B(a)P
317
Pery
--
2810
--
--
DBA
17.7
--
--
IPyr
53.8
--
--
a(g,h,i)P
.
.
.
-78400 2 210 76.5 767
.
extraction and DMSO/pentane separation, is given in Table 3. No correction for extraction efficiencies and losses has been made, since the results reported here are merely intended to be a survey, and also for reasons cited previously. Because of this, the values reported may be relatively low. For the samples from the two refineries, Site A and Site B, the number of priority PNA pollutants detected and the concentrations of those found, are in general greater in Site B than Site A. Particularly, very much higher concentrations of benzo(a)pyrene, pyrene and phenanthrene were found at Site B. This could be because Site B was emitting a greater amount of PNAs. This assertion could have been quite easily substantiated by further samplings. However, we were not able to obtain any further air samples from the site. The other possible explanation would be the distribution of PNAs containing particulates in relation to the distance from the units. At Site A we sampled directly alongside of the units whereas, at Site B, we had to sample at some distance away from the units. Fortuitously, we may have sampled at the peak of the distribution of Site B. For the July 1982 sampling, the results from the regular high volume air samples are tabulated in Table 4, while those from the cascade filters are
Polynuclear aromatic compounds in oil refinino areas
203
TABLE 4 Concentration
of PNAs
Found
o n A i r Filters A f t e r S o x h l e t E x t r a c t i o n . C o l l e c t e d J u l y 1982 (in n g 1 0 0 m - 3 A i r )
Site C
Site A Unit I
Compound
C1
C2
C3
6.1
7-4
7.0
11.3
.
.
.
.
.
1-3
1.9
--
Acen
.
.
.
.
.
3.3
3.2
3.5
Flor
4"0
4'1
4'3
5.1
Phen
.
.
8'4
4.0
12'2
.
.
0'8
0'3
1"4
22.9
4'8
8.1
Pyre 1,2-BA Chry
.
--
Unit 2 A21 A22
A12
Acyn
Flur
--
All
Naph
Anth
--
C4
.
.
.
.
.
24.1
--
5.2
. .
.
.
--
--
3"0
0-6
--
--
--
1-6
16"3
8'0
8-6
28"0
--
79.7
31.2
24"7
71-4
80'1
25-1
--
8"8
--
--
10-8
25-2
2'1
15"9
B(b)F, B(k)F
25"6
--
29.3
--
--
61-6
42"8
32-3
B(a)P
19.5
34-8
26.1
. .
.
.
.
.
.
50.9
DBA
.
.
.
.
.
IPyr
--
--
9.6
--
--
25.0
--
--
B(g,h,i)P
--
--
24-5
--
--
38.2
23.0
--
given in Tables 5 and 6. The number of priority PNA pollutants detected and their amounts were very similar at both units. Dibenzanthracene seems to be negligible at both units, while 1,2-benzanthracene was present in greatest amount. At Site C, the number of priority PNA pollutants detected was much less in almost all four samples, except for C1. The amount of those detected was also much less than those found in the refineries. The amount of 1,2-benzanthracene was also high at Site C and, in fact, comparable to those found in the refineries. It is interesting to note, though, that the 1981 samples at Site A did not indicate the presence of any of this PNA at all. Also in 1981, the variability in the number and the amounts of priority PNAs found at the same site was much greater than in 1982. The results for the cascade impactor, with paper filters, are tabulated in Tables 5 and 6. For the first 48-h sample, the PNAs were found in the filters of smaller sizes while, for the second 48-h samples, they were found on all of the filters. Also it seems that the PNAs with very low, or very high, molecular weights were less commonly found. The variability in terms of the distribution of PNAs found on different size filters was great, especially in the first 48-h sample. The variability in the total concentration of PNAs detected was much less. Again, 1,2-dibenzanthracene was present at highest concentration. The first 48-h sample (AC1) of air was monitored in essentially the same vicinity as samples A l l and A12 at Unit 1. If one ignored
204
D. L. Karlesky
e t al.
TABLE 5 Concentration
o f P N A s F o u n d o n C a s c a d e F i l t e r s o n D a y s 1 a n d 2. C o l l e c t e d J u l y 1 9 8 2 (in ng 100m -3 Air)
Days I and2 (AC1) Compound
Size,(lO > 10 10-4.9
Naph
--
Acyn
.
4.9-2.7
--
2"7-1"3 1.3--0.61
--
.
5-0
. .
.
--
.
.
.
.
<0.61
Total
5.0
9.9
.
Acen
.
Flor
--
Phen
--
Anth
.
Flur
--
--
3'0
10"0
--
6-0
19'0
Pyre
--
--
5"2
6"5
--
4.3
16"0
1,2-BA
--
--
--
11.4
5"0
51.8
68"2
Chry
--
--
--
14.7
--
8"6
23"3
3'5
30'2
33"7
--
20.7
33.9
-.
--
3'5
6-9
3"5
4-8
--
--
8-2
.
.
.
3"5
.
.
.
--
.
.
.
.
B(b)F, B(k)F
.
B(a)P
--
DBA
.
IPyr
.
.
.
.
.
23"8
23"8
B(g,h,i)P
.
.
.
.
.
21'6
21 "6
--
13"2
.
.
.
.
.
.
TABLE 6 Concentration
o f P N A s F o u n d o n C a s c a d e F i l t e r s o n D a y s 3 a n d 4. C o l l e c t e d J u l y 1982 (in n g 100 m - t A i r )
Days 3 and 4 (AC2) Compound
Size (p,) > 10 10-4.9
Naph
--
Acyn
.
.
.
Acen
.
.
.
Flor
--
Phen
2"3
Anth
--
Flur
--
Pyre
2.0
1,2-BA
--
Chry
5.1
B(b)F, B(k)F
. . .
B(g,h,i)P
.
2.6
2.6 . .
.
.
.
Total
2.6
10.2
. . --
0'9
4.0
3-5
4"7
1'9
2-3
18"0
--
--
0"8
--
0"7
1.5
2.1
2'0
2-6
1.9
1'5
10.0
3'9
3.8
4.4
2.1
--
16-2
5.2
5-6
7.8
--
36-4
55.0
5'9
3.1
--
27-1
17.4
17-4
7.0 .
6.0 .
.
.
. .
. .
--
.
<0.61
1-5
3"4
.
1.3~.61
1"6
.
IPyr
2.7-1.3
2.6
B(a)P DBA
4.9 2.7
. .
. .
. .
. .
. .
. .
. .
.
.
Polynuclear aromatic compounds in oil refining areas
205
A l l and just looked at A12 and AC1, the number and concentration of PNAs detected are quite similar. If one took the average of A l l and A12 and compared it with AC1, the amounts of PNAs are, in general, slightly more on the cascade filters. However, the concentrations are still quite comparable considering possible variation. The concentrations of PNAs found for the May 1983 samples are given in Table 7. The variability among the samples was much less than in the previous year. The concentrations of PNAs found in the refineries were also less. For instance, we did not observe a high concentration of 1,2-dibenzanthracene as in the previous year. It is possible that the change in the sampling location may have contributed to these results. Table 8 lists some literature data (Sawicki et aL, 1965; Dong et aL, 1976; Fox & Staley, 1976) on concentrations of PNAs found in different kinds of air samples. The coal-tar pitch air sample, not surprisingly, reported the highest PNAs content. Only the Maryland study (Fox & Staley, 1976) corrected for losses and efficiencies. Our studies indicate that the amounts of PNAs measured at the selected refinery areas were not as high as one would expect, with the possible exception of those samples collected at Site B. The amounts of PNAs found at Site B were much higher than those found at Site C and Site A as well as the TABLE 7 Concentration of PNAs Found on Air Filters Collected May 1983 (in ng 100 m - 3 Air) After Soxhlet Extraction Site C
Site A
Unit 1 Compound
Naph Acyn Acen Flor Phen Anth
C1
C2
C3
3-8
--
3.4
--
--
--
1.2
.
.
.
.
C4
AN1
A31
A32
4.5
--
---
3.2 .
.
.
Unit 3
AN2
.
2"3
--
--
3'2
--
1.5
4-9
2-6
2-1
8.1
4"4
3"8
1.9
1.5
6-7
9-4
6-9
15-3
11"6
1.6
1.0
1.2
2-7
2.6
2.4
6.7
3'5
Flur
6.1
2.2
1.8
2-7
8.7
5.3
4.6
4-4
Pyre 1,2-BA Chry
5.4
1.6
1.5
--
8.4
4.2
3.2
5-0
1.9
--
--
--
7'8
3"3
3"5
3-8
B(b)F, B(k)F
2"6
1-9
1"2
--
10"0
3"6
4"9
4"4
11'5
8-6
5"5
7-0
14"5
13"4
8"4
11.0
--
--
.
.
B(a)P
8"7
DBA I Pyr B(g,h,i)P
. 16"3 .
. 11 "0
.
.
.
6"3 .
9.4
-13"2
-10"7
9'4 10"7
206
D . L . Karlesky et al.
TABLE $ Concentration of PNAs Found in Several Atmospheric Particle Air Samples (in ng 100 m- 3 Air) Found in the Literature Compound
Naph Acyn Acen Flor Phen Anth Flur Pyre 1,2-BA Chry B(b)F, B(k)F B(a)P DBA IPyr B(g,h,i)P
Coal-tarpitch air sample a
. . . . 400 000 80 000 900 000 830 000 70 000 --40 000 --6 000
N Y City air pollution sample b
. . . .
Baltimore Harbor Tunnel air sample c
. . . . 50 10 190 200 430 300 20 -140 90
College Park Maryland air sample c
. . . . --9 300 12 000 10 200 I 0 600 -6 600 300 ---
--410 520 460 480 -320 ----
From Sawicki et al. (1965). b From Dong et al. (1976). c From Fox & Staley (1976). a
air samples in the N e w Y o r k a n d M a r y l a n d studies. T h e c o n c e n t r a t i o n a n d the n u m b e r of p r i o r i t y p o l l u t a n t s detected in the refineries were consistently higher t h a n sites s o m e distance a w a y f r o m these refineries. W h a t this higher q u a n t i t y m a y m e a n in terms of l o n g - t e r m e x p o s u r e is o p e n to conjecture. Thus, one c a n n o t realistically rule o u t or c o n f i r m that these h i g h e r c o n c e n trations m a y be a possible cause for the higher incidences of cancers cited at the b e g i n n i n g of this paper. Also, to really a n s w e r m a n y questions, m o r e freq u e n t a n d exhaustive samplings, t a k i n g into c o n s i d e r a t i o n all o f the possible variabilities, are needed.
ACKNOWLEDGMENT The a u t h o r s gratefully a c k n o w l e d g e the D e p a r t m e n t of E n e r g y G r a n t D E A S O 5 - 8 2 E R 6 0 1 0 0 for s u p p o r t of this work. We also t h a n k the Texas Air C o n t r o l B o a r d a n d the oil refineries for technical assistance a n d p e r m i s s i o n to c a r r y o u t s a m p l i n g at their sites.
Polynuclear aromatic compounds in oil refining areas
207
REFERENCES Blot, W. J. & Fraumeni Jr, J. F. (1982). Changing patterns of lung cancer in the United States. Am. J. Epidemiol., 115, 664-73. Blot, W. J., Brinton, L. A., Fraumeni Jr, J. F. & Stone, B. J. (1977). Cancer mortality in US counties with petroleum industries. Science, 198, 51-53. Dong, M., Locke, D. C. & Ferrand, E. (1976). High pressure liquid chromatographic method for routine analysis of major parent polycyclic aromatic hydrocarbons in suspended particulate matter. Anal. Chem., 48, 368-72. Fox, M. A. & Staley, S. W. (1976). Determination of polycyclic aromatic hydrocarbons in atmospheric particulate matter by high pressure liquid chromatography coupled with fluorescence techniques. Anal. Chem., 48, 992-8. Giger, W. & Schaffner, C. (1978). Determination of polycyclic aromatic hydrocarbons in the environment by glass capillary gas chromatography. Anal. Chem., 50, 243-9. Henderson, B. E., Gordon, R. J., Menck, H., Soohoo, J., Martin, S. D. & Pike, M. C. (1975). Lung cancer and air pollution in Southcentral Los Angeles County. Am. J. Epidemiol., 101,477 88. Hoover, R. & Fraumeni Jr, J. F. (1975). Cancer mortality in US counties with chemical industries. Environ. Res., 9, 196-207. Josephson, J. (1981). Polynuclear aromatic hydrocarbons. Environ. Sci. Technol., 15, 83-85. Lee, F. S.-C., Pierson, W. R. & Ezike, J. (1980). The problem of PAH degradation during filter collection of airborne particulates--An evaluation of several commonly used filter media. In: Polynuclear aromatic hydrocarbons: Chemical analysis and biological fate, ed. by A. Bj~rseth and A. J. Dennis, 543-63. Columbus, Ohio, Battelle Press. MacDonald, E. J. (1974). Cancer of gastrointestinal tract: Epidemiological aspects. JAMA, 228, 884-6. Natusch, D. F. S. & Tomkins, B. A. (1978). Isolation of polycyclic organic compounds by solvent extraction with dimethyl sulfoxide. Anal. Chem., 50, 1429-34. Radecki, A., Lamparczyk, H., Grzybowski, J. & Halkie, J. (1978). Separation of polycyclic aromatic hydrocarbons and determination of benzo(a)pyrene in liquid smoke preparations. J. Chromatogr., 150, 527-32. Rantanen, J. (1983). Community and occupational studies of lung cancer and polycyclic organic matter. Environ. Health Perspect., 47, 325-32. Sawicki, E., Meeker, J. E. & Morgan, M. J. (1965). The qualitative composition of air pollution source effluents in terms of aza heterocyclic compounds and aliphatic and polynuclear aromatic hydrocarbons. Int. J. Air Water Pollut., 9, 291. Schimberg, R. W. (1981). Industrial hygienic measurements of polycyclic aromatic hydrocarbons in foundries. In: Polynuclear aromatic hydrocarbons: Chemical analysis and biological fate, ed. by M. Cooke and A. J. Dennis, 755-62. Columbus, Ohio, Battelle Press. Schwartz, G. P., Daisey, J. M. & Lioy, P. J. (1981). Effect of sampling duration on the concentration of particulate organics collected on glass fiber filters. Am. Ind. Hyg. Assoc. J., 42, 258--63. Walker, R. D., Connor, T. H., MacDonald, E. J., Trieff, N. M., Legator, M. S., MacKenzie Jr, K. W. & Dobbins, J. G. (1982). Correlation of mutagenic assessment of Houston air particulate extracts in relation to lung cancer mortality rates. Environ. Res., 28, 303-12.
Survey of Polynuclear Aromatic Compounds in Oil Refining Areas D. L. Karlesky, G. Ramelow,* Y. Ueno,'l"I. M. Warner Department of Chemistry, Emory University, Atlanta, Georgia 30322, USA
& Chu-Ngi Ho Department of Chemistry, East Tennessee State University, Johnson City, Tennessee 37614, USA (Received 19 August 1985; revised version received 11 February 1986; accepted 27 May 1986)
ABSTRACT Air samples in and around refinery areas were collected over a 3-year period. The results of the analysis for polynuclear aromatic compounds listed as priority pollutants by the United States Environmental Protection Agency are presented. The particulate matters in the air were collected on glass fiber filters using high volume samplers. These samples were later Soxhlet extracted with cyclohexane, and then extracted with DMSO/pentane for isolation of the polynuclear aromatic compounds. These extracts were then analyzed using gas chromatography-mass spectrometry for specified polynuclear aromatic compounds. It was found that much higher concentrations of these aromatic compounds were found in one refinery compared to another one. In general, the number of these priority pollutants detected and their * Present address: Department of Chemistry, McNeese State University, Lake Charles, Louisiana 70609, USA. t Present address: Tobacco and Health Research Institute, University of Kentucky, Cooper and Alumni Drives, Lexington, Kentucky 40506-0236, USA. 195 Environ. Pollut. 0269-7491/87/$03"50 © Elsevier Applied Science Publishers Ltd, England, 1987. Printed in Great Britain
196
D.L. Karlesky et al. concentrations were higher in sites inside the refineries relative to a site outside the refineries.
INTRODUCTION Growing concern for the quality of our environment has prompted many researchers to study the effect of air pollution on human health. Epidemiological studies have indicated that the incidences of lung cancer are higher in urban than in rural areas (Henderson et al., 1975). The higher incidences are suspected to be due to the greater amount of mutagenic compounds found in particulate matters in urban air (Walker et al., 1982). Other researchers have also shown that there seems to be a relationship between the general location of industrial pollutant sources and geographical distribution of certain types of cancer, such as gastric (MacDonald, 1974), bladder and liver (Hoover & Fraumeni, 1975) and lung (Blot & Fraumeni, 1982). In particular, a study by Blot et al. (1977) found that incidences of skin, nasal and lung cancer were higher among workers in oil refinery areas. Polynuclear aromatic compounds (PNAs) constitute an important class of chemical pollutants associated with many of these industrial areas (Henderson et al., 1975; Schimberg, 1981; Rantanen, 1983). Many of these compounds are on the United States Environmental Protection Agency (EPA) priority pollutant list, a list that comprises compounds which have been found to be ubiquitous environmental pollutants with possible potential health hazards. Many of these PNAs are known or suspected carcinogens and/or mutagens. They may also react with other common air pollutants to produce hazardous compounds (Josephson, 1981). Depending on the source of pollution, environmental mixtures of PNAs can be extremely complex. Well conceived sampling techniques, prudent separation procedures and powerful analytical instrumentation are essential for successful analysis of these environmental samples. Capillary column gas chromatography (GC), capable of very high resolution separation, has been used extensively to analyze PNAs from complex air samples (Dong et al., 1976; Giger & Shaffner, 1978; Radecki et al., 1978). A mass spectrometer (MS) can ideally serve as a detector for the identification of the eluted trace components. In this paper, we present our use of GC-MS to survey for PNAs in air samples collected in and around two oil refineries in east Texas. The area is chosen because it is well known for its large concentration of chemical and petroleum industries which are potential sources of emitters of pollutants. Moreover, this area has been reported (Blot et al., 1977) to have high incidences of cancer among its workers.
Polynuclear aromatic compounds in oil refinin9 areas
197
MATERIALS AND M E T H O D S
Chemical and reagents The PNA standards were obtained from various sources at 95~o purity or better, and were used as received. Cyclohexane and pentane (Burdick and Jackson, Muskegon, MI) and water (J. T. Baker, Phillipsburg, PA) were all H P L C grade. Dimethylsulfoxide (DMSO) (Fisher, Fairlawn, N J) was of reagent grade. All these chemicals were used as received. High purity nitrogen and helium (Pye Barker, Atlanta, GA) were also used as received.
Particle collection All particle collection was accomplished using a Sierra model 305-2000H high volume air sampler (Sierra Instruments, Carmel Valley, CA) with a constant flow controller. All samples were collected using a flow rate of 40 ft a m i n - ~ (cfm). The air sampler was fitted with glass fiber filters which can collect particles greater than 0.3 # with better than 9 9 ~ efficiency. A record of air volume was provided and a timer registered the total elapsed time. A Sierra model 235 five stage, high volume cascade impactor was used with the air sampler to measure the complete particle size distribution from 0"5-10 #. The cascade filters (No. C-230-CF) were made of paper and supplied by Sierra Instruments.
Instrumentation for analysis Gas chromatography was performed on a Hewlett Packard 5880 gas chromatograph (Avondale, PA) with a flame ionization detector (FID). A 30-m, DB-5, SE-54 coated fused silica capillary column with 0.20 m m inside diameter (J & W Scientific, Sunnyvale, CA) was used for PNA separation. Grob's splitless injector was used for sample injection. The injection port temperature was 250°C and the carrier gas was helium, with a flow rate of 50 cm s-~ at 270°C column temperature. The initial column temperature during injection was 30°C and held for 0"3 min after injection. The temperature was then raised to 270°C at a rate of 8°C m i n A Finnigan model 6000 series G C - M S (Cincinnati, OH) at Emory University was used for parts of the analysis. The same capillary column was used, but with the helium at a column linear flow velocity of 75 cm s- 1 at 270°C. Another G C - M S at Texas A&M University was also used for parts of the analysis. This one was a Hewlett Packard system (Avondale, PA) consisting of model 5710A GC, model 5980A MS and model 5933A data system. We also had our samples analyzed in parallel by Southern
198
D.L. Karleskyet al.
Research Institute (Birmingham, AL) using the same column type and instrument conditions.
Air sampling Three separate air sampling trips were made to the same area of east Texas. The dates were: 16 August 1981, 26 July 1982 and 9 May 1983.
16 August 1981 sampling Samples were collected at two oil refineries: Site A and Site B. At Site A, samples were collected directly on two units. Unit 1 was a vacuum distillation unit where partially refined crude oil was further graded by vacuum distillation. After consultation with the industrial hygienist at the refinery, the sampling apparatus was placed near a p u m p room, where the various grades of oil were pumped to different destinations in the refinery. We were informed that one of the oil grades, No. 2 fuel oil, pumped through this room would probably contain PNAs. One 48-h high volume sample (AI) was collected here. The second unit, Unit 2, sampled at Site A, was a catalytic cracking unit. The sampler was placed almost directly beneath the cracking tower. A 24-h high volume air sample (A2) was collected here. At the other refinery, Site B, samples were collected approximately 100 yards away from a vacuum distillation unit in a relatively open area. Two samples, B 1 and B2, were collected over two consecutive 48-h periods.
26 July 1982 sampling In July 1982, sampling was repeated at the same locations at Site A. Air samples were also taken at Site C, a Texas State Air Control Experimental Station not too far away (within a 5-mile radius) outside the refineries. We had 4 days of sampling done using three high volume samplers. One sampler was at Site C collecting four consecutive 24-h samples (C1-C4). At Unit 1 of Site A, one of the air samplers was fitted with a cascade impactor collecting two 48-h samples at the same time. Simultaneously, also at Unit 1, in the vicinity of the cascade impactor, two consecutive 24-h samples (A11, A12) were gathered. On the third day, this air sampler was moved to Unit 2, and two consecutive 24-h samples (A21, A22) were also collected there.
9 May 1983 sampling Sampling was carried out again at Site A. However, due to new safety regulations, sampling directly on the units was not permitted. Therefore, sampling was moved to a location near Unit 1, about 25 yards away from the previous sampling site. Two 24-h samples, AN1 and AN2, were col-
Polynuclear aromatic compounds in oil refining areas
199
lected here. Unit 2 was not in operation during this sampling trip, so two 24-h samples (A31, A32) were taken near another cracking unit (Unit 3) in the refinery. Again, four consecutive 24-h samples (C1-C4) were collected at the same site, Site C, outside the refinery at the Texas State Air Control Experimental Station.
Sample handling Immediately after sample collection, the used filters and cartridges were wrapped in aluminum foil and stored in a freezer until sample preparation and analysis. All the particulate samples on glass fiber and cascade filters were Soxhlet extracted by folding them to fit in the extractor with 300 ml of cyclohexane. The extraction was run for 24 h with the solvent recycling every 15 min, or so. The extracts were concentrated by rotary evaporation to near dryness and then redissolved to 10 ml solutions in cyclohexane. For the samples collected in 1981, half of the final 10ml was further separated using a DMSO/pentane extraction procedure described by Natusch & Tomkins (1978). From this, a final 1 ml solution was submitted for G C - M S analysis at Texas A&M University using the Hewlett Packard system. The other half of the 10ml extract was reduced to i ml and sent to Southern Research Institute for G C - M S analysis using selective ion monitoring (SIM). For the samples collected in 1982, the final volume from the extract was reduced to 0.20 ml and again sent to Southern Research Institute for G C - M S analysis. For those collected in 1983, the final volume of the Soxhlet extract was reduced to 1 ml and analyzed on the Finnigan 6000 G C - M S without using SIM.
Chromatographictechniques A chromatogram of a standard solution of priority PNA pollutants on the SE-54 coated fused silica capillary column, using F I D detection, is used as a reference for identification of the compounds. The components of the standard solution are listed in Table 1. The oven temperature has been programmed to obtain optimum resolution. Although not shown here, the resolution was good even for several isomers, or c o m p o u n d pairs, which are difficult to resolve; for example, phenanthrene and anthracene, benzo(b)fluoranthene and benzo(k)fluoranthene. The 1981 samples were partly analyzed on the Texas A & M University Hewlett Packard G C - M S using the same fused silica column as on our GC. When a GC total ion chromatogram of 2 pl of Soxhlet extract of the PNAs standard solution was obtained, the peak shape and the resolution of the
D. L. Karlesky et al.
200
TABLE 1 Standard PNA Solution and Its Components Abbreviations used in this manuscript
Full name
1. Naph 2. Acyn 3. Acen 4. Flor 5. Phen 6. Anth 7. Flur 8. Pyre 9. 1 , 2 - B A 10. Chry 11. B ( b ) F 12. B(k)F 13. B ( a ) P 14. Pery 15. IPyr 16. DBA 17. B ( g , h , i ) P
Naphthalene Acenaphthylene Acenaphthene Fluorene Phenanthrene Anthracene Fluoranthrene Pyrene 1,2-Benzanthracene Chrysene Benzo(b)fluoranthene Benzo(k)fluoranthene Benzo(a)pyrene Perylene Indeno(1,2,3,-c,d)pyrene 1,2,5,6-Dibenzanthracene Benzo(g,h,i)perylene
higher molecular weight compounds were poorer than using FID. To improve the selectivity and sensitivity, SIM was applied, and all the components were then resolved and detected. The ions monitored at different time intervals are tabulated in Table 2. The value of the technique was more evident when an air sample was analyzed. For a G C / F I D chromatogram of an air sample which had been Soxhlet extracted, although one could try to match the retention times of peaks of the chromatogram with that of the P N A standard solution, it was difficult to obtain quantitative measurements. The same difficulty was encountered when a GC total ion c h r o m a t o g r a m of the same air sample was taken. The poor resolution would not permit one to obtain any reliable qualitative identification and quantitative results. However, when we acquired the SIM chromatogram of the same sample under identical chromatographic conditions, we could detect all of the seventeen PNAs due to greater selectivity and sensitivity of the technique. These procedures and parameters were used in all subsequent analyses.
Filters and quantitative analysis A number of workers have investigated the use of filters for particulate sampling. Schwartz and co-workers (1981) conducted a study which sug-
Polynuclear aromatic compounds in oil refining areas
201
TABLE 2 Mass to Charge Ratios Monitored for Analysis of Priority PNA Pollutants Time interval
role
Compound
1-13 min
128 152 154 166
Naph Acen Acyn Flor
14~26 min
166 178 202 222
Phen, Anth Pyre 1,2-BA Chry
27-38.5 min
202 228 252
Flur, Pyre Chry, 1,2-BA B(b)F, B(k)F, B(a)P, Pery
39-end
252
B(b)F, B(b)F, B(a)P, Pery
276 278
IPyr, B(g,h,i)P DBA
gested that loss of analytes could occur if glass filters were used for sampling over an extended period (24-h and more). Lee et al. (1980) carried out comprehensive studies of particulate sampling using different types of filters. They found that recoveries of the same PNA, benzo(a)pyrene were quite different on those filters. They found that filters with Teflon binders; for example, polytetrafluoroethylene (PTFE) filters, had better recoveries than the glass filters. They proposed that the surface properties of the glass filters leading to catalysis, affinity and uptake of moisture and reactivity, could account for loss, degradation and transformation of the analytes. However, they found that the PTFE Teflon filters unfortunately contained more fluorescent background impurities in their extracts. Therefore, it is extremely difficult to be able to be rid of any spurious effects and to reproducibly account for losses and efficiencies. From our experience, we agree with these remarks. Therefore, we do not account for losses and efficiencies. This is consistent with our goal of providing a general survey of the PNA content in oil refining localities.
RESULTS A N D DISCUSSION The apparent total concentration, in ng 100 m-3 air, of each PNA on the priority pollutant list found on the filters collected in 1981, after Soxhlet
D. L. Karlesky e t al.
202
TABLE 3 Concentration Pentane
of PNAs
Found
on Air Filters After Soxhlet and DMSO/
Extraction. Collected August
1981 (in ng 100 m-3 Air)
Site A
Compound Naph
Unit 1 ,41 .
Site B Unit 2 .42
.
Acyn
.
Unit 1 BI
Unit 2 B2
.
--
--
--
1.8
--
--
373
Flor
11.8
248
Phen
--
913
Acen
85"6 15 2 0 0
79-3 3 360
Anth
--
4.1
343
290
Flur
--
57.7
503
1 020
Pyre
--
356
2 770
1 880
--
--
118 160
1,2-BA
5.1
Chry
--
--
--
B(b)F' 1 B(k)F)
38.9
--
1 400
B(a)P
317
Pery
--
2810
--
--
DBA
17.7
--
--
IPyr
53.8
--
--
a(g,h,i)P
.
.
.
-78400 2 210 76.5 767
.
extraction and DMSO/pentane separation, is given in Table 3. No correction for extraction efficiencies and losses has been made, since the results reported here are merely intended to be a survey, and also for reasons cited previously. Because of this, the values reported may be relatively low. For the samples from the two refineries, Site A and Site B, the number of priority PNA pollutants detected and the concentrations of those found, are in general greater in Site B than Site A. Particularly, very much higher concentrations of benzo(a)pyrene, pyrene and phenanthrene were found at Site B. This could be because Site B was emitting a greater amount of PNAs. This assertion could have been quite easily substantiated by further samplings. However, we were not able to obtain any further air samples from the site. The other possible explanation would be the distribution of PNAs containing particulates in relation to the distance from the units. At Site A we sampled directly alongside of the units whereas, at Site B, we had to sample at some distance away from the units. Fortuitously, we may have sampled at the peak of the distribution of Site B. For the July 1982 sampling, the results from the regular high volume air samples are tabulated in Table 4, while those from the cascade filters are
Polynuclear aromatic compounds in oil refinino areas
203
TABLE 4 Concentration
of PNAs
Found
o n A i r Filters A f t e r S o x h l e t E x t r a c t i o n . C o l l e c t e d J u l y 1982 (in n g 1 0 0 m - 3 A i r )
Site C
Site A Unit I
Compound
C1
C2
C3
6.1
7-4
7.0
11.3
.
.
.
.
.
1-3
1.9
--
Acen
.
.
.
.
.
3.3
3.2
3.5
Flor
4"0
4'1
4'3
5.1
Phen
.
.
8'4
4.0
12'2
.
.
0'8
0'3
1"4
22.9
4'8
8.1
Pyre 1,2-BA Chry
.
--
Unit 2 A21 A22
A12
Acyn
Flur
--
All
Naph
Anth
--
C4
.
.
.
.
.
24.1
--
5.2
. .
.
.
--
--
3"0
0-6
--
--
--
1-6
16"3
8'0
8-6
28"0
--
79.7
31.2
24"7
71-4
80'1
25-1
--
8"8
--
--
10-8
25-2
2'1
15"9
B(b)F, B(k)F
25"6
--
29.3
--
--
61-6
42"8
32-3
B(a)P
19.5
34-8
26.1
. .
.
.
.
.
.
50.9
DBA
.
.
.
.
.
IPyr
--
--
9.6
--
--
25.0
--
--
B(g,h,i)P
--
--
24-5
--
--
38.2
23.0
--
given in Tables 5 and 6. The number of priority PNA pollutants detected and their amounts were very similar at both units. Dibenzanthracene seems to be negligible at both units, while 1,2-benzanthracene was present in greatest amount. At Site C, the number of priority PNA pollutants detected was much less in almost all four samples, except for C1. The amount of those detected was also much less than those found in the refineries. The amount of 1,2-benzanthracene was also high at Site C and, in fact, comparable to those found in the refineries. It is interesting to note, though, that the 1981 samples at Site A did not indicate the presence of any of this PNA at all. Also in 1981, the variability in the number and the amounts of priority PNAs found at the same site was much greater than in 1982. The results for the cascade impactor, with paper filters, are tabulated in Tables 5 and 6. For the first 48-h sample, the PNAs were found in the filters of smaller sizes while, for the second 48-h samples, they were found on all of the filters. Also it seems that the PNAs with very low, or very high, molecular weights were less commonly found. The variability in terms of the distribution of PNAs found on different size filters was great, especially in the first 48-h sample. The variability in the total concentration of PNAs detected was much less. Again, 1,2-dibenzanthracene was present at highest concentration. The first 48-h sample (AC1) of air was monitored in essentially the same vicinity as samples A l l and A12 at Unit 1. If one ignored
204
D. L. Karlesky
e t al.
TABLE 5 Concentration
o f P N A s F o u n d o n C a s c a d e F i l t e r s o n D a y s 1 a n d 2. C o l l e c t e d J u l y 1 9 8 2 (in ng 100m -3 Air)
Days I and2 (AC1) Compound
Size,(lO > 10 10-4.9
Naph
--
Acyn
.
4.9-2.7
--
2"7-1"3 1.3--0.61
--
.
5-0
. .
.
--
.
.
.
.
<0.61
Total
5.0
9.9
.
Acen
.
Flor
--
Phen
--
Anth
.
Flur
--
--
3'0
10"0
--
6-0
19'0
Pyre
--
--
5"2
6"5
--
4.3
16"0
1,2-BA
--
--
--
11.4
5"0
51.8
68"2
Chry
--
--
--
14.7
--
8"6
23"3
3'5
30'2
33"7
--
20.7
33.9
-.
--
3'5
6-9
3"5
4-8
--
--
8-2
.
.
.
3"5
.
.
.
--
.
.
.
.
B(b)F, B(k)F
.
B(a)P
--
DBA
.
IPyr
.
.
.
.
.
23"8
23"8
B(g,h,i)P
.
.
.
.
.
21'6
21 "6
--
13"2
.
.
.
.
.
.
TABLE 6 Concentration
o f P N A s F o u n d o n C a s c a d e F i l t e r s o n D a y s 3 a n d 4. C o l l e c t e d J u l y 1982 (in n g 100 m - t A i r )
Days 3 and 4 (AC2) Compound
Size (p,) > 10 10-4.9
Naph
--
Acyn
.
.
.
Acen
.
.
.
Flor
--
Phen
2"3
Anth
--
Flur
--
Pyre
2.0
1,2-BA
--
Chry
5.1
B(b)F, B(k)F
. . .
B(g,h,i)P
.
2.6
2.6 . .
.
.
.
Total
2.6
10.2
. . --
0'9
4.0
3-5
4"7
1'9
2-3
18"0
--
--
0"8
--
0"7
1.5
2.1
2'0
2-6
1.9
1'5
10.0
3'9
3.8
4.4
2.1
--
16-2
5.2
5-6
7.8
--
36-4
55.0
5'9
3.1
--
27-1
17.4
17-4
7.0 .
6.0 .
.
.
. .
. .
--
.
<0.61
1-5
3"4
.
1.3~.61
1"6
.
IPyr
2.7-1.3
2.6
B(a)P DBA
4.9 2.7
. .
. .
. .
. .
. .
. .
. .
.
.
Polynuclear aromatic compounds in oil refining areas
205
A l l and just looked at A12 and AC1, the number and concentration of PNAs detected are quite similar. If one took the average of A l l and A12 and compared it with AC1, the amounts of PNAs are, in general, slightly more on the cascade filters. However, the concentrations are still quite comparable considering possible variation. The concentrations of PNAs found for the May 1983 samples are given in Table 7. The variability among the samples was much less than in the previous year. The concentrations of PNAs found in the refineries were also less. For instance, we did not observe a high concentration of 1,2-dibenzanthracene as in the previous year. It is possible that the change in the sampling location may have contributed to these results. Table 8 lists some literature data (Sawicki et aL, 1965; Dong et aL, 1976; Fox & Staley, 1976) on concentrations of PNAs found in different kinds of air samples. The coal-tar pitch air sample, not surprisingly, reported the highest PNAs content. Only the Maryland study (Fox & Staley, 1976) corrected for losses and efficiencies. Our studies indicate that the amounts of PNAs measured at the selected refinery areas were not as high as one would expect, with the possible exception of those samples collected at Site B. The amounts of PNAs found at Site B were much higher than those found at Site C and Site A as well as the TABLE 7 Concentration of PNAs Found on Air Filters Collected May 1983 (in ng 100 m - 3 Air) After Soxhlet Extraction Site C
Site A
Unit 1 Compound
Naph Acyn Acen Flor Phen Anth
C1
C2
C3
3-8
--
3.4
--
--
--
1.2
.
.
.
.
C4
AN1
A31
A32
4.5
--
---
3.2 .
.
.
Unit 3
AN2
.
2"3
--
--
3'2
--
1.5
4-9
2-6
2-1
8.1
4"4
3"8
1.9
1.5
6-7
9-4
6-9
15-3
11"6
1.6
1.0
1.2
2-7
2.6
2.4
6.7
3'5
Flur
6.1
2.2
1.8
2-7
8.7
5.3
4.6
4-4
Pyre 1,2-BA Chry
5.4
1.6
1.5
--
8.4
4.2
3.2
5-0
1.9
--
--
--
7'8
3"3
3"5
3-8
B(b)F, B(k)F
2"6
1-9
1"2
--
10"0
3"6
4"9
4"4
11'5
8-6
5"5
7-0
14"5
13"4
8"4
11.0
--
--
.
.
B(a)P
8"7
DBA I Pyr B(g,h,i)P
. 16"3 .
. 11 "0
.
.
.
6"3 .
9.4
-13"2
-10"7
9'4 10"7
206
D . L . Karlesky et al.
TABLE $ Concentration of PNAs Found in Several Atmospheric Particle Air Samples (in ng 100 m- 3 Air) Found in the Literature Compound
Naph Acyn Acen Flor Phen Anth Flur Pyre 1,2-BA Chry B(b)F, B(k)F B(a)P DBA IPyr B(g,h,i)P
Coal-tarpitch air sample a
. . . . 400 000 80 000 900 000 830 000 70 000 --40 000 --6 000
N Y City air pollution sample b
. . . .
Baltimore Harbor Tunnel air sample c
. . . . 50 10 190 200 430 300 20 -140 90
College Park Maryland air sample c
. . . . --9 300 12 000 10 200 I 0 600 -6 600 300 ---
--410 520 460 480 -320 ----
From Sawicki et al. (1965). b From Dong et al. (1976). c From Fox & Staley (1976). a
air samples in the N e w Y o r k a n d M a r y l a n d studies. T h e c o n c e n t r a t i o n a n d the n u m b e r of p r i o r i t y p o l l u t a n t s detected in the refineries were consistently higher t h a n sites s o m e distance a w a y f r o m these refineries. W h a t this higher q u a n t i t y m a y m e a n in terms of l o n g - t e r m e x p o s u r e is o p e n to conjecture. Thus, one c a n n o t realistically rule o u t or c o n f i r m that these h i g h e r c o n c e n trations m a y be a possible cause for the higher incidences of cancers cited at the b e g i n n i n g of this paper. Also, to really a n s w e r m a n y questions, m o r e freq u e n t a n d exhaustive samplings, t a k i n g into c o n s i d e r a t i o n all o f the possible variabilities, are needed.
ACKNOWLEDGMENT The a u t h o r s gratefully a c k n o w l e d g e the D e p a r t m e n t of E n e r g y G r a n t D E A S O 5 - 8 2 E R 6 0 1 0 0 for s u p p o r t of this work. We also t h a n k the Texas Air C o n t r o l B o a r d a n d the oil refineries for technical assistance a n d p e r m i s s i o n to c a r r y o u t s a m p l i n g at their sites.
Polynuclear aromatic compounds in oil refining areas
207
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