Occurrence of nitro-pah in the atmosphere in a rural area

~mmphkc Emvirmmwnr Vol. 18. No. IO, pp. 2159-2165. 1984 Riated in Glut Britain

oow-6981164 53.00 + 0.00 G 1984 Fwgamon Press Ltd.

OCCURRENCE OF NITRO-PAH IN THE ATMOSPHERE IN A RURAL AREA

TORBEN NIELSEN and BERNHARD SEITZ

Chemistry Department, Ris@ National Laboratory, DK-4ooo Roskilde, Denmark

and

THOMAS RAMDAHL

Central Institute for Industrial Research, P.O. Box 350, Blindren, Oslo 3, Norge

(First received 25 October 1983 and received for publication 14 March 1984)

Abstract-By means of gas chromatography with nitrogen sensitive detection and negative ion chemical ionization mass spectrometric detection 7 mononitro-PAH, 9-nitroanthracene, x-nitro-4,5-methylenephenanthrene, 3-nitrofluoranthene, l- and tnitropyrene, lO-nitrobettx(a)anthracene and bnitrobenxo- (a)pyrene have been identied in samples of airborne particulate matter. Furthermore, 8-nitrotluoranthene has been tentatively identified. The amounts of mononitro-PAH are one to two orders of magnitude lower than the most common carcinogenic PAH, as e.g. benao(a)pyrene. Filter effects have been studied, 9- nitroanthracene can be transformed during sampling at low atmospheric concentrations of NO, and photochemical oxidants to 9,lOdinitroanthracene and 10-nitroanthrone.

Key word index: Polycyclic aromatic hydrocarbons, nitroderivates of polycychc aromatic hydrocarbons, atmosphere, exhaust gases, sampling artifacts.

1. INTRODUCTION

As early as the 1950s it was observed that a significant part of the carcinogenic compounds present in organic extracts of collected airborne particulate matter did not belong to the class of polycyclic aromatic hydrocarbons (PAH) (Falk et al., 1960). Several recent investigations seem to show that only a minor part of the mutagenic activity in Salmonella tests of organic extracts of airborne particulate matter can be ascribed to the presence of PAH (van Cauwenberghe and van Vaeck, 1983; Madsen et al., 1982; Pitts, 1983; Pitts et al., 1982). Laboratory experiments have shown that some PAH as well as some substituted PAH may be transformed in the atmosphere to their nitro derivatives by reaction with NOz and HN03 (van Cauwenberghe and van Vaeck, 1983; Nielsen et al.,

1983b; Nielsen, 1984; Pitts, 1983). Furthermore, bio- logical tests indicate that a significant part of the so- called directly acting mutagenic compounds present in extracts of airborne particulate matter is nitro-arenes (Lofroth, 1981; Pitts et al., 1982; Talcott and Harger, 1981; Wang et al., 1980). But only little is known about the identity of these compounds (D’Agostino et al., 1983; Gibson, 1982; Nielsen, 1983a.b; Nielsen, et al., 1983a).

This paper presents the results from an investigation of the presence of mononitro-PAH and PAH in the atmosphere in a rural area. Rural samples were studied, as atmospheric processes could have caused transformation of PAH to nitro-PAH during the transport

in the atmosphere, and filter artifacts should be less important in rural samplescompared to urban samples considering the lower atmospheric concentrations of NO*. Six mononitro-PAH (9-nitroanthracene (9-NA), 3-nitrofluoranthene (3-NF), I-nitropyrene (I-NP), 2- nitropyrene (2-NP), IO-nitrobenz(a)anthracene (10- NElaA) and &ritrobenzo(a)pyrene @NBaP) were identified by means of gas chromatography (GC) with nitrogen-sensitive (NP) detection (Nielsen, 1983a; Ramdahl et al., 1982) and GC with negative ion chemical ionization mass spectrometric (NICIMS) detection (Ramdahl and Urdal, 1982). One isomer of nitro+-methylenephenanthrenes (x-NMP) was identified by GC with NICIMS detection. In addition, the presence of three of these (9-NA, l-NP and lO- NBaA) were determined in 30 24-h samples.

2. EXPERIMENTAL

Determination of PAH and nitro-PAH

24-h samples of airborne particulate matter corresponding to c. 2000 m3 were collected using conventional’ Hi-Vol samplers with glass fibre filters (Whatmann G/FA). The samples were extracted ultrasonically 3 x Mmin with SOml dichloromethane (Merch, Lichrosolv) each time. The concentrated solutions were fractionated by means of high- performance liquid chromatography (HPLC) using a mixture of n-hexane (Merck zur Riickstandsanalys) and benzene (Merck, pa.) in a ratio of 3: 1 as eluent. The flow-rate was 3.0 ml min - ’ . The columns (12 cm x 4.6 mm (pm-column) + 25 cm x 8.0 mm) were packed with Nucleosil-S-50-5. The fractions consisting of PAH and mononitro-PAH were

2159

2160 TORBEI~ NIELSEN YI al

collected and concentrated to 1.0 ml and lot) pl. respectively. The amounts of 23 PAH were determined by CC with flame- tontzatton (FI) detection. and those of 9NA. I-NP and IO- NBaA by CC with NP detection. The method is described in more detail elsewhere (Nielsen, 1983a).

The mononitro-PAH fracttons from 20 samples were combined and purified by means of HPLC in order to remove transformation products formed during the storage of the samples. The HPLC system used was the sameas described in the prevtous section. The purified mononttro-PAH fractton was analyzed by CC with NP-detection. The gas chromatog- raph, Carlo Erba 2900, was equipped with on-column inJectton and connected to a KtppZonen BD 9 recorder. The fused silica column used was coated with SE-54 (Hewlett- Packard) (25 m x 0.32 mm i.d.). The oven temperature was programmed from 75 to 90 C at 15 min ’ and from 90 to 300 Cat 10 min-‘. In addition, the sample was analyzed by CC with NICIMS detection. The sample mtroduction was accomplished by means of a Fmnipn 9610 gas chromato- graph directly interfaced to the mass spectrometer by the 30 m x 0.25 mm i.d. DB-5 fused silica-column (J. .k W. Scientific. Inc.). The CC conditions were as follows: iniector temperature 28OC; interface 24O‘C; column temperature IO&325 Cat 5‘min-‘: the initial temperature was held for 3 min. The Finnigan model 4021 quadropole mass spectrometer was equipped with a standard electron impact, chemical ionization (Cl) source. Primary ionization of the Cl reagent gas was accomplished using a 70 eV beam of electrons generated from a heated rhenium filament with an emission current of 0.25 mA. Methane was used as reagent gas. The application of NICIMS detection for identification of nitro-PAH is described in more detail elsewhere (Ramdahl and Urdal, 1982).

3. RESULTS AND DISCUSSION

Idenrifcarion by CC with NP-detection

The purified mononitro-PAH fraction from twenty samples of airborne particulate matter was analyzed by GC with NP-detection. Six of the components in the sample giving response on the NP-detector had exactly the same retention times as the following nitro-PAH; 9-NA. 3-NF. 8-NF, l-NP. IO-NBaA and 6-NBaP. Neither I-nitro- nor 3nitrobenzo(a)-pyrene was observed in the sample. A chromatogram of the sample is shown in Fig. 1. No quantitative determination of the six nitro-PAH was performed, since the 20 samples had been stored for more than 6 months, and even at - 18-C degradation of at least some nitro-PAH may occur. In most of the 30 24-h samples a nitrogen- containing component having the same retention time as 2-NP was present and in some cases in higher amounts than l-NP. These results were, however, neglected at that time, since nitration of pyrene in conventionel nitration reactions exclusively occurs in l-position (Dewar et al., 1956; Radner, 1983). The amounts of 2-NP were, however, determined in six of the samples. The amount of 2-NP (mean +2-u) was 0.02 f 0.02 ng m- 3. The corresponding amounts of 9- NA, I-NP and lO-NBaA were 0.05 + 0.04,O.Ol k 00.1 and 0.03 f 0.02 ng m - 3, respectively.

Identification by CC with NICIMS-detection

In addition, the purified mononitro-PAH fraction

5 10 15 20 25 TIME (min)

Fig. 1. GCchromatogram with NP- detection ofa sample ofairborne particulate matter. The identity of the peaks: 9-NA: 9- nitroanthracene, 3-NF: 3_nitrofluoranthene, 8-NF: I-nitrofluoranthene, I-NP: l-nitropyrene. IO-NBaA: lO-nitrobenz(a)- anthracene. 6-NBaP: 6_nitrobenzo(a)-

pyrene.

was analyzed by GC with NICIMS detection. The chromatogram is shown in Fig. 2. Six mononitro-PAH having identical retention time and identical mass spectra with those of standard compounds were identified by this technique.

The two chromatograms by the two different detection modes are quite different. The analysis by NICIMS-detection was performed two months later than the analysis by NP-detection. Although the

TIME

0.00 6.20 16.LO 25.00 33.20 Ll.LO 50.00 58.20

II I I 1 I 1 ! /

I , I 1 I 1 I I 0 500 1000 1500 2000 2500 3000 3500

SCAN

Fig. 2. GCchromatogram with NICIMSdetection of a sample of airborne particulate matter. Identity of the peaks: 9-NA: 9-nitroanthracene, M, = 235: x-nitro-4,5- methylenephenanthrene, 3-NF: 3-nitrofluoranthene, l-NP: I-nitropyrene, 2-NP: 2-nitropyrene, IO-NW IO- nitrobenz(a)anthracene, 6-NBaP: 6_nitrobertzo(a)pyrene.

Occurrence of nitro-PAH in the atmosphere in a rural area 2161

mononitro-PAH probably has different relative response factors by the two different detection techniques, we consider that the major reasons are (a) differences in the injection technique and injection temperature (Ramdahl et ol., 1982a), (b) degradation of the mononitro-PAH during the two months storage and during the transport for the differences in the chromatograms.

One of the mononitro-PAH, 8-NF, identified by means of NP-detection was unobserved in the sample using NICIMS-detection. Figure 3(a) shows the chromatogram of five mononitro-PAH standards with a molecular weight of 247 using GC with extracted ion current NICIMS-detection at m/z 247. In Fig. 3(b) using the same technique the presence of 3-NF, l-NP. and 2-NP in the sample is shown, but neither 4- nitropyrene nor 8-NF was observed. Figure 3(c) shows the chromatogram of the sample using the total ion current detection mode.

In addition to the six mononitro-PAH identified by means of GC with NICIMS-detection a mononitro- PAH having a molecular weight of 235 was observed (see Fig. 2). The nitro group is identified by the m/z 46 ion (Ramdahl and Urdal, 1982). Nitration of 4,5- methylenephenanthrene by dinitrogen tetraoxide (Radner, 1983) gave four isomers. One of these had exactly the same retention time and identical mass spectrum with the mononitro-PAH in the air sample

TIME 33.20 3410 35.00 3 5.50 36.40

~~“‘I”~~~~“~~“~~I

100.0 - 2-NP

3-NF

1 4-NP I

l-NP

‘3-NF ’ (bl]

t

‘3-NF 497.2

1

I r 17, ” I 1 #A 2000 2050 2100 2l50 2200

SCAN

Fig. 3. GCchromatograms with NICIMS-detcction, (a) with extracted ion current (m/r = 247) of a mixture of five standards of nitrofluoranthenes (NF) and nitropyrene (NP), (b) with extracted ion current (m/z = 247) of a sample of airborne particulate matter, (c) with total ion current of the sample of airborne

particulate matter.

with a molecular weight on m/z 235. Further work is in progress in order to determine the position on the nitro group in the identified x-NMP.

Discussion

Six mononitro-PAH (9-NA, 3-NF, l-NP, 2-NP, IO- NBaA and 6-NBaP) had been identified in samples of airborne particulate matter by two different detection techniques. Their presence in these types of samples must, therefore, be considered to be unambiguous. 9- NA has been identified by others in samples of airborne particulate matter by means of GC with single-ion-monitoring using a mass spectrometer with electron impact ionization (Brorstriim et 01.. 1983). 3- NF, l-NP and 6-NBaP have been identified after reduction to the corresponding amines by thin-layer chromatography (Jiiger, 1978) and HPLC (Gibson, 1982) with fluorescence detection. Furthermore, 9-NA, l-NP and 3-NF have been identified in urban air particles collected during a period of months by GC with NICIMS-detection (Ramdahl et al., 1982b). In addition, I-NP and 6-NBaP have been identified in several types of emission sources, stack gases from aluminium smelters (Oehme et al., 1982) and wood stoves, gasoline (Gibson, 1982) and diesel exhaust gases (Paputa et al., 1983; Schuetzle et al., 1982). Furthermore, 9-NA and 3-NF have been identified in diesel exhaust gases (Paputa et al., 1983). Neither 2-NP nor lO-NBaA appear to have been demonstrated to be present in any types of environmental samples so far.

The identification of 8-NF in samples of airborne particulate matter must at present be considered to be tentative, although this compound has been detected in samples from diesel exhaust gases (Paputa et al., 1983).

The last of the identified mononitro-PAH, x-NMP has, apparently, not been described in the literature.

The identification of 2-NP in samples of airborne particulate matter is most interesting suggesting that mononitro-PAH may be formed in the atmosphere or during sampling by a chemical pathway totally different from the conventional nitration of mechanism of PAH (Nielsen, 1983b, 1984). 2-NP has not been

detected in diesel exhaust gases suggesting that its concentration in these types of samples is at least two orders of magnitude lower than that of l-NP (Paputa et ol., 1983). This, apparently indicates that high temperature processes can be excluded as a source for formation of 2-NP in post combustion gases (Nielsen, 1981; Nielsen et al., 1983b, Schuetzle et al., 1983), and that at least only a minor part of the 2-NP should originate from emission sources. Neither does it appear plausible that 2-NP is formed in the atmosphere by nitration of photolytic activated pyrene, as the solar intensity was low.

It has been suggested earlier that non-ionic reactions by vapour phase as well as particle-associated PAH induced by radicals perhaps could lead to the formation of mononitro-PAH in the atmosphere (Nielsen, 1981; Nielsen et al., 1983b) accordingly to the scheme

2162 TORBEN NIELSEN YI al.

H

& ’ @ H+x.- (0 ,

H

6?? No2 / o

0, --wx

H X

H

i NOI

NO1

Corr~~nding to this, monoaro~ti~ as e.g. toluerte,

have been demonst~t~ to be nitrated by subsequent reactions with OH radicals and NOz (Kenley et af., 1978; Atkinson et al., 1980).

The l-position is the most reactive site in the pyrene molecule towards radicals (Dickermann et al., 1973; Herndon, 1981), and it may, therefore, be possible that subsequent reactions of pyrene with a radical and NGz could end up by yielding 2-NP as the final product. Thus, a possible explanation for the presence of 2-NP in samples of airborne particulate matter is that it is formed in the atmosphere by a sequence of reactions as suggested in the scheme.

Occurrence of nitro-PA H

Thirty 24-h samples of airborne particulate matter were collected in the period February-April 1982 in a rural area, 30 km west of Copenhagen. Theamounts of three mononitro-PAH and 23 PAH were determined in all the samples. In addition, the amounts of some particle-associated inorganic components as well as some gaseous components were determined. The results are shown in Table 1.

As discussed later, the amounts of mononitro-PAH determined in the colkected samples do not appear to represent the true concentrations of these compounds in the atmosphere. Nevertheless it has been preferred to express the amounts in the collected samples in ng rns3, as atmospheric concentrations of PAH most usually are expressed in this unit. Experiments using different sampling times showed that transformation of the 23 PAH during sampling was insi~i~~ns, and the determined amount of the PAH in the collected samples should, therefore, represent the true concentrations of these compounds in the atmosphere. The samples had been collected at low ambient temperature (mostly in the range - 10 to + 10°C) and at low concentrations of NO2 and photochemical oxidants in the atmosphere.

The amounts of the mononitro-PAH in the collected samples are typically one to two orders of magnitude lower than those of the most common carcinogenic PAH: cycio~nteno(cd)pyrene, ~nz(a~nthra~ne~

Table I. Presence of mononitro-PAH, PAH and tnorgantc co-pollutants in 30samples ofairborne particulate matter and

the concentrations of some gaseous pollutants

Compound

9-Nitroanthracene I-Nitropyrene l~Nitro~nz(a~nthracene Phenanthrene Anthracene I-Methylphenanthrene Fluoranthene Pyrene Benzo(b)naphtho-

(2,1-d)thiophene Cyclopenteno(c,d)pyrene Benz(a)anthracene Chrysene + triphenylene Benzo(b, j and k~uo~nthene Benzo(e)pyrene Benzo(a)pyrene Perylene Indeno(l,2,3+xI)pyrene 1,2,5,6_Dibenzanthracene Benzo(ghi)perylene Anthanthrene Coronene Nitrate Sulphate Chloride Acids Lead Vanadium Nickel Nitrogen oxides Nitrogen dioxide Sulphur dioxide Ozone

Concentrations*

Meant ?a --

0.03F0.01 ngm ’ 0.009 * 0.005 0.014 + 0.007

0.4 + 0.2 0.05 2 0.02 0.09 rt: 0.04

1.2 +0.6 -- 1.3kO.8 -

0.11 + 0.05 0.2fO.l 0.4kO.2 1.2~0.5 1.3+o.s 0.6iO.2 -- 0.6 rt: 0.2

0.09f0.04 -1 0.7 f 0.2 --.

0.14*0.08 .- 0.6kO.2 -.

0.08~0.04 - 0.24f0.06 -

1.7kO.2 PgNm-’ 2.8 f 0.4 PgSm-” 2.0f0.6 /cgme3 1956 neqv m-’ 9Oi10 ng me3 17fl ~-

7,0io.s ~~ 16&4 ppb 13t3 -- 9*3 --

22*4 --

* 24-h mean values.

benzo(b)- and benzo( j)fluoranthene, ~nzo~a~pyrene, indenof 1,2,3-~~yrene, and 1,2,5,b~i~n~nthra&ene. So far, only few data on the presence of mononitro- PAH in samples of airborne particulate matter are available. The amounts of I-NP in samples collected in city air in the Detroit area corresponded to 0.016-0.030ng me3 (Gibson, 1982), i.e. 2-3 times higher than the mean value found in this investigation. The ratio of I-NP to pyrene and of I-NP to benzo(af- pyrene were both 0.02 in the 24 h samples from Detroit. The corresponding mean ratios were a bit lower in the samples at Ris+$, 0.007 and 0.015.

It should be borne in mind, however, that signifi~nt amounts of pyrene, especially at higher ambient tem- peratures, may be present in vapour phase in ambient air (Thrane and Mikalsen, 1981), and thereby the ambient temperature will affect the ratio of particulate I-NP to pyrene. The samples in the Detroit area were collected in June (Gibson, 1981), while those at Risql in February, March and April. Thus, the difference in the determined I-NP: P ratios can be explained by means of differences in the ambient temperature, although other factors also may have contributed, and the

Oaxxrence of nitro-PAN in the atmosphere in a rural area 2163

results from the two investigations appear to agree reasonably well.

Sources for PAW and nitro-PAH

The only local source of PAH ~llut~on of import- ance at Ris@ is car exhaust. However, the PAH protiles of the samples show that car exhaust gases have not been the dominant source of PAH pollution. If this had been the case, one should expect ratios ( f 2a) of ~clo~nteno(~~yrene to benx(a)anthracene, of ~nzo(ghi~~lene to ~~o(e)pyrene and of coronene to benzo(e)pyrene on 4&2, 1.9fO.6 and 1.3 It0.2, respectively (Grimmer et al., 1980). The observed mean ratios were much lower, 0.5, 1.0 and 0.4, respectively, indicating that much less than 50% of the PAH originated from automobiles.

The low ratios of particulate nitrate to NUs, and of particulate sulphate to SO2 show that transformation of neither SO2 nor NO1 had occurred to a significant extent during the transport in the atmosphere. This and the high ratio between NOz and NO, indicate that most of the inorganic N compounds and S compounds originate from meso-scale transport. As the sources for atmosphere pollution with NO, and St& are the same as those for atmospheric pollution with PAH, it appears that most of the PAW originates from meso- scale transport from different sources, including car exhaust gases. The levels of PAH were generally 2odfl% of those that are typical for city air in ~~navia in winter time (Lindskog and &orstrlim, 1981; Madsen et al., 1982; Olufsen and Alfheim, 1980) Correspondingly, the levels of NO, + NO; and SOz +SO:- are about 2-4 times lower than those observed in city air (Jensen et a!., 1980).

The mean ratio of benxo(a)pyrene to benxo(e)pyrene of 1.0 indicates that transfor~tjon of reactive PAH in the atmosphere and during sampling had occurred to only a limited extent. Otherwise, one should expect this ratio to be much lower than 1.0 (Brorstriim et al., 1983; Grimmer et al., 1980; Nielsen, 1984; Nielsen et al., 1983b). Thus, under winter conditions the transformation rate of PAH during the first 24 h after emission appears to be slow.

The transformation rate of SO2 to particulate sulphate depends on the meteorological conditions and the atmospheric composition of oxidizing species (Rohde et al., 1981). Although the deposition rates of SO2 and particulate sulphate show variations under different conditions, one can use the ratio of particulate sulphate to total anthropogenic S (St& + SO:-) as 8 relative measure of the transport time of the polluted air masses and the extent of atmospheric processes. Anthropogenic sulphate concentrations can be attained by correcting the sulphate values for a cont~bution from m~time sources. This ~nt~bution can be estimated by means of the particulate Na content (Riley and Skirrow, 1975). In this investigation the ~rit~econt~bution was negligible except in four cases. In these it was 935% of the total content of

sulphate, Least squares analyses of the ratio lO- NBaA : BaA vs the proportion of particulate anthropo- genie sulphate to the total content of anthropogenic S gave a significant correlation (I -- 0.62; P < 0.01). This appears to suggest either that lO-NBaA mostly originates from transfo~tion of ~nz(a~nthra~ne in the atmosphere or is formed as an artifact during sampling. The latter is also Possible as the formation rate of nitro-PAH during sampling appears to be higher on aged aerosols than on fresh aerosols (Brorstrom et nL, 1983; Nielsen, 1981; Nielsen et al., 1983b). lO-NBaA so far has not been ~dent~~ in any types of samples from stack and exhaust gases and at least its concentration in diesel exhaust gases appears to be very low (Paputa et al., 1983). This also suggests that it originates mostly from formation in the atmosphere or during sampling.

T$a~~~r~t~~~ af 9-~~tr~~~thra~e~e ~~r~~g sarn~~~~g

ft has been demonstrated in other investigations that nitro-PAH may be formed from PAH during sampling in ambient air (Brorstriim et al., 1983; van Cauwenbergheand van Vaeck, 1983; Pitts, 1983), while it has not been ~v~ti~t~ whether nitro-PH may be t~sfo~~ during sampling Exe~imen~ were, therefore, performed with loaded filters spiked with 9- NA. The ambient temperature had been relatively low (about -t- IOOC) and the concentrations of photochemical oxidants and nitrogen dioxide are in the same magnitude as in Table 1. These experiments were performed after 24-h sampling using two Hi-V01 samplers, one of the filters was spiked with a solution of 4.14 mg 9-NA in dichloromethane, and the other with dichloromethane. When the filters were dry the sampling was continued for 24 h, afterwards the filters were extracted ultrasonically with dichloromethane. The concentrated solutions were analyxed using GC with game-ionization detection as well as NP- detection. Two products were identified by means of their retention times, 9,I~initroanthr~ne and lO- nitroanthrone. In addition, 4 unknown products were observed. The results from one of the experiments are shown in Table 2. Most of the 9-NA appears to have disappeared from the filters by blow-off. The experiments show that 9-NA and perhaps also other nitro- PAH may be transformed by nitration as well as

Table 2. Transformation of Pnitroanthracene during sampling

Unspiked Spiked Yield Compound fitter fiber (7;)

9-Nitroantbmcenc 0.2 395 9.6 9,10-Dinitroantbracenc 2.6 19 IO-Nitroanthrom < 0.02 1.5 E3 Ant~quinone 0.08 3.7 0.09t Anthrone < 0.05 < 0.08 <8x lo-& Four unknown products 0.4 0.01 Rest (blow-OK) 90

*Spiked with 4.14 mg 9-nitroantbracene, t Content in 9-n~tr~tb~n~ 0,05x.

oxidation during sampling, l-NP appears to be more stable (Grosjean et nl., 1983) than 9-NA. As most of the 9-NA probably had been adsorbed to the filter surface and not to the surfaces of the particulates, the experiments cannot be used to evaluate the rates of these processes. The amount of nitrogen~ontaining com-

pounds with the same retention time as 9,10_dinitro- anthracene was much higher than the content of 9-NA in the unspiked sample (Table 2). But as no fraction- ation procedure was used before analyzing the sample by GC, it may be possible that this peak also contained other nitrogen-containing compounds besides 9,10-dinitroanthracene. It can only be concluded that the amount corresponding to the difference between the spiked and unspiked sample must be ascribed to 9,10-dinitroanthracene formed during sampling from 9-NA.

CONCLUSIONS

Seven mononitro-PAH have been identified in samples of airborne particulate matter, and 8-NF has been tentatively identifi~. Neither x-NMP, 2-NP nor lO-NBaA have been demonstrated to be present in any types of environmental samples before. The presence of 2-NP suggests perhaps that mononitro-PAH may be formed also by non-ionic radical reactions in the atmosphere.

The concentrations of mononitro-PAH in atmospheric samples are one to two orders of magnitude lower than the most colon carcinogenic PAH, including benzo(a)pyrene. Formation as well as transformation of mononitro-PAH during sampling may occur.

Acknowledgements-Financial support from the Danish Ministry of Energy and from the Nordic Council of Ministers through the Joint Nordic Project MIL-2 is gratefully ac- knowledged. The dete~iMtions of the atmospheric concentrations of particfe-asseciated and gaseous inorganic eom- ponents were performed by Anne Maria Hansen, Kare Kemp and Bjame West&erg, Danish Air Pollution Laboratory. 2- NP (Hansen and Berlb 1981) was synthesized by Ame Berg Chemistry Department, University of Arhus, and 9-NA, 3- NF, S-NF, 6-NBaP and x-NMP were synthesized by Ole Jdrgensen and Susanne Petersen.

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Occurrence of nitro-pah in the atmosphere in a rural area

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