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Gaseous and particulate polycyclic aromatic hydrocarbons (PAH) from the marine atmosphere
aoo44981/84 s3.00 + 0.00
Amospkric hthmmmr Vol. IS. No. IO,pp. 2183-2190, 1984 Printed10 GrePtBntain.
Pqamon PressLtd.
GASEOUS AND PARTICULATE POLYCYCLIC AROMATIC HYDROCARBONS (PAH) FROM THE MARINE ATMOSPHERE J. C. MARTY, M. J. TISSIER and A. SALIOT* Laboratoire de Physique et Chimie Marines de YUniversitCPierre et Marie Curie, LA CNRS 353, Tour 24, 4 Place Jussieu, 75230 Paris Cedex 05, France (First received 12 February
1984)
Abstract-Despite their importance in environmental studies, there are very few data concerning the gaseous polycyclic aromatic hydrocarbons (PAH) in the marine atmosphere and their potmtial importance. We present here concentrations and distributions for gaseous and particulate PAH sampled in the atmosphere over the Tropical and Equatorial East Atlantic. After collection respecting ultra-clean conditions, PAH were isolated and analysed through capillary GC and Cc/MS. Concentrations of gaseous PAH ranged from 7 to 18 ngm-“. They are an order of magnitude higher than those encountered for particulate PAH. This enhances the importana of gaseous PAH vs PAH associated with aerosols and strongly shows their mode in transport and ocean-atmosphere exchange processes. Gaseous PAH are composed almost entirely of extremely volatile compounds such as phenanthrene. On the other hand, aerosol PAH distributions exhibit a predominance of phenanthrene, but also contain substantial amounts of other PAH: fluoranthene, pyrene, chrysene, benzofluoranthenes and benzopyrenes. The comparisov between the distributions of PAH and their alkylated homologues, both in the atmosphere and the sea surface microlayer collected in the same area, suggests a mixed origin for the gaseous PAH: non-combusted petroleum residues and pyrolytic-like compounds emitted from the ocean.
INTRODUCTION
Polycyclic aromatic hydrocarbons (PAH) are widespread contaminants of the environment. They are issued from petroleum products or generated by the pyrolysis of these petroleum products and of other combustibles such as wood and coal. Thus, pyrolytic PAH are mostly associated with industrial activities and, for this reason, their concentration in the environment has greatly increased since the beginning of industrialization (- 100 years). Non industrial combustion of organic matter (forest fires, agricultural burning, . . . ) also contributes significantly to the production of PAH (NAS, 1972). Thus, the sources of PAH are mostly on continents and the main route for their transfer to the ocean is through the atmosphere followed by rain scavenging and/or dry deposition. They are also delivered to natural waters by runoff. Atmospheric PAH have been principally studied in urban and suburban areas (see the reviews of Neff, 1979; Simoneit and Mazurek, 1981; Tissier, 1981). Most of these studies were conducted to monitor PAH concentrations because of their suspected toxicity. Some concentrations of PAH from the marine atmosphere have been reported by Ketseridis et al . (1976), Lunde and Bjijrseth (1977), Daisey et al. (1981) and by out group: Marty et al. (1978), Tissier (1981), H8 (1982), Ha et al. (1984). These results deal with
* Author to whom correspondana should be sent.
PAH concentrations from aerosols, but, there is very little information about gaseous PAH concentrations in the marine atmosphere, probably due to the difficulties of sampling and analysing these compounds in trace amounts without analytical contamination. We present in this paper the fitst concentrations and distributions obtained for gaseous PAH sampled in the Tropical and Equatorial East Atlantic. We compare these data to the PAH content of atmospheric particulates, of surface microlayer particulates and dissolved matter from the same oceanic area, in order to determine the origin of PAH and the nature of the transit from their sources.
EXPERIMENTAL
(1) Samples Samples were collected during two oceanographic cruises: MIDLANTE on the R/V Jean charcot (May1974, Tropical East Atlantic) and ROMANCAP on the R/V Canricome (May-June lb77, Equatorial East Atlantic), &e Fii. 1. The nature of samples and the meteorological conditions prevailing during collection are summarized in Table 1. Particulate atmospheric samples were collected by filtering large volumes of air (500-1500 m3) through Whatman GF/C glass fibre filter mounted in a metallic filter holder. Gaseous products were collected on polyurethane foam plugs, 15 cm long+5 x 5 cm cross section, plaad behind the filter holder in a metalliccontainer. The two collectors were connected to the pump (Dolky type, flow rate 12 m3 h-l) using 20 m of vinyl tubing. The volume of air filtered was known exactly by means of a glass flow meter located in line 1 m before the pump.
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:----
-._._
Fig. 1. Sampling locations. 0 Reference station for surface microlayer water.
Table 1. Atmospheric sampling conditions encountered during Midlante (MI) and Romancap (RO) cruises Sample MI (particles)
RO 1 (gaseous)
RO 2 (gaseous)
Date
Air volume
2614315174 3 000 m’ (2 filters)
wind speed direction air T”C water T”C
: 11 m s-’
31/5-2/6/77
wind speed direction air T”C water T”C
: 7.1 m s-’
wind speed direction air T”C water T”C windspeed: direction air T”C water T”C wind speed direction air T”C water T”C windspeed: direction air TC water T”C
: 7.3 m s- ’
24/6/77
523 m3
540 m3
RO 4 (gaseous)
68/6/77
535 m3
RO 5 (gaseous
8-10/6/77
486 m3
l&12/6/77
434 m3
& particulate)
RO 6 (gaseous)
Meteorological Data :NE : 25 : 22 :SE : 25.4 : 25.2 :SE : 25.4 : 25.4 4.9ms-’ : S E. SSE : 24.1 : 24.1 : 3.8 m s- ’ : SSE : 24.5 : 25.0 7.5ms-’
: ssw : 25.8 : 26.8
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Gaseous and particulate polycyclic aromatic hydrocarbons (PAH) To avoid risks of contamination from the ship, a number of precautions were taken for sampling The sampling unit was located 5 m forward of the ship’s bow and about i m above sea level; the pump operated about 20m behind the filter holders was electrically connected to a wind direction monitor which interrupted all sampling when the wind deviated more than a sector of 30” on either side of the direction in which the ship was pointing. At no time was the pump in operation while the ship was stationary. The material which was collected on the polyurethane foam plug was called gaseous material, although it contained small-size particles passing through the glass fiber filter. A collection efficiency of 98 % for particles whose diameter is > 0.03 pm was proposed by Butcher and Charlson 1972 for this type of filter. The retention efficiency of gaseous material by polyurethane foam is about 90% for compounds with molecular weight > 200, for a sampling time of 24 h (600 m’ of air), as shown by Simon and Bidleman in 1979 for chlorinated hydrocarbons. Filters and polyurethane foam plugs were carefully precleaned by extraction of organic impurities with methylene chloride in a soxhlet apparatus. Collection of subsurface (0.2m) seawater by immersing glass carboys and of surface microlayer (0.4 mm thick) by a metallic screen has already been described by Marty et al . (1979). Seawater samples were immediately filtered onboard the ship through precleaned Whatman GF/C glass fibre filters. Dissolved lipids (including PAH) were extracted from filtered water with chloroform. Extracts, filters and polyurethane foam plugs were kept frozen ( - 20°C) until analysis in the laboratory. (2) Analyses Lipids were extracted from particulate material (from air and water) for 24 h in a soxhlet apparatus using a 1: 1 mixture of benzene and methanol. Gaseous lipids were extracted from foams with chloroform. Gaseous and particulate lipid extracts from air, dissolved and particulate lipid extracts from seawater were then treated by the same procedures. The extracts were saponified with KOH under N,. The unsaponifiable material was fractionated by adsorption chromatography on silicic acid and alumina columns and elution with a mixture of solvents of increasing polarity (Saliot et a/., 1982). PAH were then analysed by gas chromatography (GC) using glass capillary column coated with SE 52 and by GCmass spectrometry (CC-MS) as described by Tissier and Saliot (1983). In the CC analysis, concentrations of PAH were obtained by comparison of sample peak areas with those of known amounts of standards (dioctyl phthalate, phenanthrene, fluoranthene, chrysene, benm(a)pyrene and perylene) run under the same analytical conditions. CC-MS analyses, performed on a LKB 9OOS/PDP 11 El0 computer unit, permitted the analysis of parent PAH and their alkylated homologues from m/e = 178 (phenanthrene and anthracene) to m/e = 300 (coronene). Detailed conditions were described by Tissier and Saliot (1983). The quantification of individual compounds was performed using dioctyle phthalate (DOP) as internal standard in the following manner: knowing the absolute concentration of DOP from GCanalyses. the ratio between individual PAH and DOP concentrations was determined by computerized CC-MS whichallowed theabsoluteconcentration of PAH to be determined. There was a good agreement (better than 90%) between GC and CC-MS responses for the main components that were measured using standards (DOP, phenanthrene, fluoranthene, chrysene, benzo(a)pyrene and perylene). RESULTS Total PAH concentrations are reported in Table 2: gaseous and particulate PAH from the atmosphere,
Table 2. PAH concentrations from atmosphere (rig m- ‘)and water (ng I- ‘) Gaseous
Particulates
RO 1 R02 R04 ROS R06
7 18 11 10 18
n.a. ,. ..
MI
n.c.
0.2
Dissolved
Particulates
35.2 6
15 9
Sample Atmosphere Romancap Guinea Gulf
Midlante Cape Verde Islands Sea water Romancap microlayer subsurface water
0.1 n.a.
n.a., Not analysed. n.c., Not collected.
dissolved and particulate
PAH from microlayer and subsurface water. Major PAH and their alkylated homologues have been determined. In order to illustrate the relationship between the air and water samples, we present in Fig. 2 the relative distribution of major PAH for an atmospheric sample representative of the air over the Equatorial Atlantic, and from microlayer both for dissolved and particulate species. The major compounds identified are: phenanthrene (Ph), fluoranthene (Fl), pyrene (Py), chrysene + triphenylene + benzo (a)anthracene (Ch), benzo (j)and benzo (k)fluoranthene (BF), benzo (a)pyrene and benzo(e)pyrene (BP) and perylene (Pe); the structures of the principal compounds identified are shown in Fig 3. In Fig. 4, the distributions of alkylated (Cl to C4) homologues of phenanthrene are reported for atmosphere and water samples, for the site preceedingly chosen from the Equatorial Atlantic.
DISCUSSlON Gaseous and particulate PAH concentrations
Concentrations of gaseous PAH in the atmosphere range from 7 to 18 ng m- 3 for the five samples analysed (Table 2). These data are the first, to our knowledge, obtained for atmospheric gaseous PAH over remote pure marine areas. For the same samples, gaseous nalkanes exhibited also a narrow concentration range: 33 to 86 ngm-’ (Marty, 1981). Surprisingly, particulate PAH concentrations for the atmosphere were much lower. Among our samples, only two were analysed successfully, due to minute amounts obtained and the quantity required for analysis. Concentrations determined (0.1 and 0.2 ngm-‘) were lower than those reported by Ketseridis et al. (1976), 11 ngme3 for atmospheric Atlantic aerosol samples or by Lunde and Bjiirseth (1977) who gave values of 0.1-7 ng m- 3 for individual
2186
f
Ph
FI
Py Ch
R05
8F
BP Pe
Gaseous
Ph I=1 f’y Ch 8F BP P&! RO
5 Partlculete
Ph FI MiCrOlayer
DiSSolved
Mlcratayer
Py
Ch BF BP R Particulate
Fig. 2. Relative ~st~butions ( ?A of major PAH from atmospheric sample RO 5 and microlayer water (dissolved and ~~iculate). k Series extending beyond perylene. Ph = phenanthrene; Fl = ~uoranthene; Py = pyrene; Ch = chtysene + t~ph~ykne + ~~~a~anthr~~e; BF = henze(j) + ~~~k)fluoranth~e; BP = benzo(a)pyrcne + ~~de)pyr~e; Pe = perylene.
PAH in Norwqian marine air. Gagosian et a!. (1982) found no indi~id~i PAN con~tration > 5 pgm - 3 in aerosols from the Tropical North Pacific. PAH concentrations that we present for aerosols collected over the Atlantic are much lower than those obtained for continental atmosphere: 6 ng m- 3 for the air collected over a forest from the Ivory Coast (Tissier, 1981) or for particles from urban or suburban areas: near Los Angeles (Gordon, 1976); 5-26ngm-3 OS-l.1 ngmv3 (individual PAH) in air over Great Lakes, U.S.A. (Eisenreich et al., 1981); 30 ng m - 3 in air masses collected over Sweden ori~nating from France and England (Lunde and Bjerseth, 1977); i-52.?ngmv3 inairover Norwayand0.5-92.4ngm-3 in air over Sweden (Ejiirseth et al., 1979); and others (Lao et ul., 1973; 19’75;Dong et al., 1976; Lee et al., 1977; Van Vaeck and Van Cauwenberghe, 1978). From data presented in Table 2, it appears that PAW are essentially (more than 90 %) gaseous in the atmosphere, This fractionation between gaseous and partictdate PAH is about the same as that encountered for n-afkanes, reviewed by Marty (1981) and Duce and Gagosian (1982). The predominance of gaseous PAH in the marine atmosphere was not expected since PAW are introduced into the atmosphere in particulate form (NAS, 1972) and tend to remain associated with particles, in
contrast with PCB’s for which at least 8Op, is transported in gaseous form (Bidleman et al., 1977). Such a ~~orni~n~ of gaseous PAH has been preceedingly noted by Cautreeh and Van Cauwenberghe (1978) for continental atmospheres. They indicated values for the distribution factor between the particulate and the gas phase samples varying from 0.027 for phenanthrene and anthra~~, 0.488 for pyrene up to 11.5 for ~nzo(k)fluoranthene and ~~o~b)fluoranthene. Van Vaeck and Van Cauwenberghe (1978) have collected suburban aerosols, separating particulates as a function of particle size. They have shown that 95 f, of PAH was in the size class =z 3 pm and 60-70 3, was associated with particles c f pm. The data of Pierce and Katz (1975) and Katz and Pierce (1976) indicated that PAN are transported in the atmosphere principally in association with sub-pm particles (those particles which are not eflicientiy scavenged by rain, Lodge er uf., 1981). For ~rine~rosols, a very few data are avaiiable, Ha et al. (1984) have recently shown that the eoncentrationsof PAH as a function of particle size over the Mediterranean Sea was characterized by a maximum for particles _ 1.5 Brn in diameter; but the pyrolytic-iike fractions were associated with smaller size aerosols. Further examination of PAH distributions are necessary to determine the true state of PAH in the marine atmosphere: really gaseous or
Gaseous and particulate
&
Pv
(PAH)
2187
pyrene
f luoranthene
triphenylene
Ch
chryrene
BF
benzo(
j )
6
benro( l() f luoranthene
BP
benzo(
e)pyrene
benzo(a)pyrene
Pe
hydrocarbons
anthracene
phensnt hrene
Ph
FI
polycyclic aromatic
benz (ajanthracen.2
parylcne
Fig. 3. Structures of major
associated with very small-size particles, not retained by glass fibre filters. In order to reach the sampling sites (more than 1000 km from coasts in some cases here), ‘gaseous’ PAH must be less subjected to photo-oxidation than the rate predicted by laboratory models. This hypothesis is not new, as some in vitro experiments have shown that photo-oxidation may be slow for some PAH in the presence of oxygeneted derivatives such as phenols present in the atmosphere, or finally by singlet oxygen capture by complex metallic ions, as discussed by Neff (1979). Distribution and nature of PAH in the atmosphere Gaseous PAH. Distributions of major PAH, gaseous and associated with particles are different as
PAH
and abbreviations used.
shown in Fig. 2, for the representative sample R05 (other samples have respectively exactly the same distributions). Gaseous PAH are mostly constituted by the most volatile compound (phenanthrene). This repartition is consistent with the remarks of Junge (1977) and Marty (1981). They showed that a compound having a vapor pressure value up to lo- 5 mm Hg might be present as gases in the atmosphere. This happens for phenanthrene, whose vapor pressure value is 6.8 x 10W4mm Hg (Handbook of Chemistry and Physics, 1972-73), but not for heavier molecular weight compounds; for example, pyrene (vapor pressure 6.8 x lo- ’ mm Hg). The distribution of alkylated components, as an example in the phenanthrene series (Fig. 4) is dominated by the parent compound and would suggest a
2188
J. C
MART\
PI ui
The distribution of major PAH as well as that of alkylated homologues of phenanthrene (FIN. 4) supgests, as for gaseous PAH. a mixed nature: pyrolyttclike PAH and petroleum-like PAH. These distnbutions cannot be only explained by a partitionlnp ot PAH emitted in the continental atmosphere by man’s activity between gaseous and particulate phases. The analysis of the nature of PAH in surface waters will give further evidence for the ‘oceanic ortgm’ of atmospheric PAH.
R05 Part:culate
Origin of PAH in the atmosphere
/“\ / \
0.5
b
l> I +a 0.51 Microlayer D~esolvcd
Microlayer Particulate
Fig. 4. Distributions of alkylated homologues (Cl -C4) of phenanthrenc (normalized to phenanthrenc) for sample ROS and microlayer water, for dissolved and particulate species.
fossil fuel combustion origin for these PAH. But it is known that petroleum hydrocarbons produce a distribution maximizing at the C3 or C4 alkyl homologue (Wakeham and Farrington, 1980) and if, due to fractionation processes at the sea-air interface (or in the atmosphere), the lighter molecular compounds are favoured during evaporation, we cannot exclude a partly petroleum origin for these compounds. Particulate PAH. Marine aerosols PAH distributions (Fig. 2) exhibit the predominance of phenanthrene, but also the presence of other PAH such as tluoranthene, pyrene, chrysene, benzofluoranthenes and benzopyrenes) at non negligible concentrations. Two main differences can be mentioned, existing between this repartition and those observed for urban and suburban aerosols (i) the absence of perylene, which is not surprising, this compound being of land origin, (Aizenshtat, 1973) and the absence of compounds with molecular weight > 252 and (ii) the relative abundance of phenanthrene. Phenanthrene was not detectable or reported in very low concentrations in urban aerosols by Gordon (1976) and Van Vaeck and Van Cauwenberghe (1978). Bjdrseth et al. (1979) reported large concentrations of phenanthrene, but without predominance over other PAH in the atmosphere over the Atlantic.
In order to determine the possible relationship between PAH from the atmosphere and from sea water, PAH have been analysed in the sea surface microlayer from the same area. As shown in Fig. 2, the distributions of PAH both dissolved and associated with particles are different. Low molecular weight PAH (phenanthrene and fluoranthene) predominate in the dissolved fraction. This could be explained by the higher solubility of these compounds with respect to higher molecular weight PAH. The preferential solubility explains also the distribution of alkylated homologues of phenanthrene in the dissolved fraction (Fig. 4). On the other hand, the particulate PAH distribution (Fig. 2) and the distribution of alkylated homologues maximizing at C3-C4 species suggest strongly a noncombusted petroleum-type material (Wakeham and Farrington, 1980). From this type of petroleum residue which is common in most of oceanic areas (Burns and Villeneuve, 1983), evaporation would lead to a relative increase of components having the highest vapor pressure values: phenanthrene and its alkylated derivatives, fluoranthene. Thus, two origins can be proposed for gaseous PAH identified in the open ocean atmosphere (i) evaporation of particulate pyrolytic-like PAH emitted into the atmosphere over continents and (ii) evaporation of pyrolytic-like or non-combusted petroleum accumulated at the sea-air interface. In the two cases the modification of PAH characteristics by physicochemical processes in the water phase such as preferential solubilization of light compounds and nonalkylated derivatives, may assist in the repartition of PAH observed both in sea water (dissolved phase) and aerosols. The origin of PAH in the particulate form is more difficult to define. The resemblance between particulate PAH from the atmosphere and dissolved PAH from the sea surface microlayer suggests that PAH from aerosols are probably emitted from the sea by bubble bursting process, which introduces droplets of sea water into the atmosphere. We cannot totally rule out the hypothesis of a direct input to the marine atmosphere of terrestrial dusts (like those analysed by Laflamme and Hites, 1978), whose PC-H distributions would be very close to that of atmosphere samples we have analysed, in agreement with previous observations by Simoneit and Eglinton (1977) who indicated
Gaseous and particulate polycyclic aromatic hydrocarbons (PAH)
the presence of lipid molecules typical of continental soils in dusts collected in the same oceanic area as our samples. Nevertheless, the analyses presented in Figs 2 and 4 strongly suggest that both unburned petroleum PAH accumulated in the sea surface microlayer essentially as particulates and pyrolytic-like compounds fractionated in the ocean according to their solubilities, are emitted into the atmosphere faster than continental dusts are deposited. A separation of aerosols as a function of particle size such as realised recently by H6 et al. (1984) and the systematic collection of dusts would be useful to differentiate between the net fluxes of both pyrolytic-like petroleum-derived PAH at the sea-air interface.
and
Acknowledgements-We are grateful to Dr. K. Bums for helpful comments on the manuscript.
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Amospkric hthmmmr Vol. IS. No. IO,pp. 2183-2190, 1984 Printed10 GrePtBntain.
Pqamon PressLtd.
GASEOUS AND PARTICULATE POLYCYCLIC AROMATIC HYDROCARBONS (PAH) FROM THE MARINE ATMOSPHERE J. C. MARTY, M. J. TISSIER and A. SALIOT* Laboratoire de Physique et Chimie Marines de YUniversitCPierre et Marie Curie, LA CNRS 353, Tour 24, 4 Place Jussieu, 75230 Paris Cedex 05, France (First received 12 February
1984)
Abstract-Despite their importance in environmental studies, there are very few data concerning the gaseous polycyclic aromatic hydrocarbons (PAH) in the marine atmosphere and their potmtial importance. We present here concentrations and distributions for gaseous and particulate PAH sampled in the atmosphere over the Tropical and Equatorial East Atlantic. After collection respecting ultra-clean conditions, PAH were isolated and analysed through capillary GC and Cc/MS. Concentrations of gaseous PAH ranged from 7 to 18 ngm-“. They are an order of magnitude higher than those encountered for particulate PAH. This enhances the importana of gaseous PAH vs PAH associated with aerosols and strongly shows their mode in transport and ocean-atmosphere exchange processes. Gaseous PAH are composed almost entirely of extremely volatile compounds such as phenanthrene. On the other hand, aerosol PAH distributions exhibit a predominance of phenanthrene, but also contain substantial amounts of other PAH: fluoranthene, pyrene, chrysene, benzofluoranthenes and benzopyrenes. The comparisov between the distributions of PAH and their alkylated homologues, both in the atmosphere and the sea surface microlayer collected in the same area, suggests a mixed origin for the gaseous PAH: non-combusted petroleum residues and pyrolytic-like compounds emitted from the ocean.
INTRODUCTION
Polycyclic aromatic hydrocarbons (PAH) are widespread contaminants of the environment. They are issued from petroleum products or generated by the pyrolysis of these petroleum products and of other combustibles such as wood and coal. Thus, pyrolytic PAH are mostly associated with industrial activities and, for this reason, their concentration in the environment has greatly increased since the beginning of industrialization (- 100 years). Non industrial combustion of organic matter (forest fires, agricultural burning, . . . ) also contributes significantly to the production of PAH (NAS, 1972). Thus, the sources of PAH are mostly on continents and the main route for their transfer to the ocean is through the atmosphere followed by rain scavenging and/or dry deposition. They are also delivered to natural waters by runoff. Atmospheric PAH have been principally studied in urban and suburban areas (see the reviews of Neff, 1979; Simoneit and Mazurek, 1981; Tissier, 1981). Most of these studies were conducted to monitor PAH concentrations because of their suspected toxicity. Some concentrations of PAH from the marine atmosphere have been reported by Ketseridis et al . (1976), Lunde and Bjijrseth (1977), Daisey et al. (1981) and by out group: Marty et al. (1978), Tissier (1981), H8 (1982), Ha et al. (1984). These results deal with
* Author to whom correspondana should be sent.
PAH concentrations from aerosols, but, there is very little information about gaseous PAH concentrations in the marine atmosphere, probably due to the difficulties of sampling and analysing these compounds in trace amounts without analytical contamination. We present in this paper the fitst concentrations and distributions obtained for gaseous PAH sampled in the Tropical and Equatorial East Atlantic. We compare these data to the PAH content of atmospheric particulates, of surface microlayer particulates and dissolved matter from the same oceanic area, in order to determine the origin of PAH and the nature of the transit from their sources.
EXPERIMENTAL
(1) Samples Samples were collected during two oceanographic cruises: MIDLANTE on the R/V Jean charcot (May1974, Tropical East Atlantic) and ROMANCAP on the R/V Canricome (May-June lb77, Equatorial East Atlantic), &e Fii. 1. The nature of samples and the meteorological conditions prevailing during collection are summarized in Table 1. Particulate atmospheric samples were collected by filtering large volumes of air (500-1500 m3) through Whatman GF/C glass fibre filter mounted in a metallic filter holder. Gaseous products were collected on polyurethane foam plugs, 15 cm long+5 x 5 cm cross section, plaad behind the filter holder in a metalliccontainer. The two collectors were connected to the pump (Dolky type, flow rate 12 m3 h-l) using 20 m of vinyl tubing. The volume of air filtered was known exactly by means of a glass flow meter located in line 1 m before the pump.
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:----
-._._
Fig. 1. Sampling locations. 0 Reference station for surface microlayer water.
Table 1. Atmospheric sampling conditions encountered during Midlante (MI) and Romancap (RO) cruises Sample MI (particles)
RO 1 (gaseous)
RO 2 (gaseous)
Date
Air volume
2614315174 3 000 m’ (2 filters)
wind speed direction air T”C water T”C
: 11 m s-’
31/5-2/6/77
wind speed direction air T”C water T”C
: 7.1 m s-’
wind speed direction air T”C water T”C windspeed: direction air T”C water T”C wind speed direction air T”C water T”C windspeed: direction air TC water T”C
: 7.3 m s- ’
24/6/77
523 m3
540 m3
RO 4 (gaseous)
68/6/77
535 m3
RO 5 (gaseous
8-10/6/77
486 m3
l&12/6/77
434 m3
& particulate)
RO 6 (gaseous)
Meteorological Data :NE : 25 : 22 :SE : 25.4 : 25.2 :SE : 25.4 : 25.4 4.9ms-’ : S E. SSE : 24.1 : 24.1 : 3.8 m s- ’ : SSE : 24.5 : 25.0 7.5ms-’
: ssw : 25.8 : 26.8
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Gaseous and particulate polycyclic aromatic hydrocarbons (PAH) To avoid risks of contamination from the ship, a number of precautions were taken for sampling The sampling unit was located 5 m forward of the ship’s bow and about i m above sea level; the pump operated about 20m behind the filter holders was electrically connected to a wind direction monitor which interrupted all sampling when the wind deviated more than a sector of 30” on either side of the direction in which the ship was pointing. At no time was the pump in operation while the ship was stationary. The material which was collected on the polyurethane foam plug was called gaseous material, although it contained small-size particles passing through the glass fiber filter. A collection efficiency of 98 % for particles whose diameter is > 0.03 pm was proposed by Butcher and Charlson 1972 for this type of filter. The retention efficiency of gaseous material by polyurethane foam is about 90% for compounds with molecular weight > 200, for a sampling time of 24 h (600 m’ of air), as shown by Simon and Bidleman in 1979 for chlorinated hydrocarbons. Filters and polyurethane foam plugs were carefully precleaned by extraction of organic impurities with methylene chloride in a soxhlet apparatus. Collection of subsurface (0.2m) seawater by immersing glass carboys and of surface microlayer (0.4 mm thick) by a metallic screen has already been described by Marty et al . (1979). Seawater samples were immediately filtered onboard the ship through precleaned Whatman GF/C glass fibre filters. Dissolved lipids (including PAH) were extracted from filtered water with chloroform. Extracts, filters and polyurethane foam plugs were kept frozen ( - 20°C) until analysis in the laboratory. (2) Analyses Lipids were extracted from particulate material (from air and water) for 24 h in a soxhlet apparatus using a 1: 1 mixture of benzene and methanol. Gaseous lipids were extracted from foams with chloroform. Gaseous and particulate lipid extracts from air, dissolved and particulate lipid extracts from seawater were then treated by the same procedures. The extracts were saponified with KOH under N,. The unsaponifiable material was fractionated by adsorption chromatography on silicic acid and alumina columns and elution with a mixture of solvents of increasing polarity (Saliot et a/., 1982). PAH were then analysed by gas chromatography (GC) using glass capillary column coated with SE 52 and by GCmass spectrometry (CC-MS) as described by Tissier and Saliot (1983). In the CC analysis, concentrations of PAH were obtained by comparison of sample peak areas with those of known amounts of standards (dioctyl phthalate, phenanthrene, fluoranthene, chrysene, benm(a)pyrene and perylene) run under the same analytical conditions. CC-MS analyses, performed on a LKB 9OOS/PDP 11 El0 computer unit, permitted the analysis of parent PAH and their alkylated homologues from m/e = 178 (phenanthrene and anthracene) to m/e = 300 (coronene). Detailed conditions were described by Tissier and Saliot (1983). The quantification of individual compounds was performed using dioctyle phthalate (DOP) as internal standard in the following manner: knowing the absolute concentration of DOP from GCanalyses. the ratio between individual PAH and DOP concentrations was determined by computerized CC-MS whichallowed theabsoluteconcentration of PAH to be determined. There was a good agreement (better than 90%) between GC and CC-MS responses for the main components that were measured using standards (DOP, phenanthrene, fluoranthene, chrysene, benzo(a)pyrene and perylene). RESULTS Total PAH concentrations are reported in Table 2: gaseous and particulate PAH from the atmosphere,
Table 2. PAH concentrations from atmosphere (rig m- ‘)and water (ng I- ‘) Gaseous
Particulates
RO 1 R02 R04 ROS R06
7 18 11 10 18
n.a. ,. ..
MI
n.c.
0.2
Dissolved
Particulates
35.2 6
15 9
Sample Atmosphere Romancap Guinea Gulf
Midlante Cape Verde Islands Sea water Romancap microlayer subsurface water
0.1 n.a.
n.a., Not analysed. n.c., Not collected.
dissolved and particulate
PAH from microlayer and subsurface water. Major PAH and their alkylated homologues have been determined. In order to illustrate the relationship between the air and water samples, we present in Fig. 2 the relative distribution of major PAH for an atmospheric sample representative of the air over the Equatorial Atlantic, and from microlayer both for dissolved and particulate species. The major compounds identified are: phenanthrene (Ph), fluoranthene (Fl), pyrene (Py), chrysene + triphenylene + benzo (a)anthracene (Ch), benzo (j)and benzo (k)fluoranthene (BF), benzo (a)pyrene and benzo(e)pyrene (BP) and perylene (Pe); the structures of the principal compounds identified are shown in Fig 3. In Fig. 4, the distributions of alkylated (Cl to C4) homologues of phenanthrene are reported for atmosphere and water samples, for the site preceedingly chosen from the Equatorial Atlantic.
DISCUSSlON Gaseous and particulate PAH concentrations
Concentrations of gaseous PAH in the atmosphere range from 7 to 18 ng m- 3 for the five samples analysed (Table 2). These data are the first, to our knowledge, obtained for atmospheric gaseous PAH over remote pure marine areas. For the same samples, gaseous nalkanes exhibited also a narrow concentration range: 33 to 86 ngm-’ (Marty, 1981). Surprisingly, particulate PAH concentrations for the atmosphere were much lower. Among our samples, only two were analysed successfully, due to minute amounts obtained and the quantity required for analysis. Concentrations determined (0.1 and 0.2 ngm-‘) were lower than those reported by Ketseridis et al. (1976), 11 ngme3 for atmospheric Atlantic aerosol samples or by Lunde and Bjiirseth (1977) who gave values of 0.1-7 ng m- 3 for individual
2186
f
Ph
FI
Py Ch
R05
8F
BP Pe
Gaseous
Ph I=1 f’y Ch 8F BP P&! RO
5 Partlculete
Ph FI MiCrOlayer
DiSSolved
Mlcratayer
Py
Ch BF BP R Particulate
Fig. 2. Relative ~st~butions ( ?A of major PAH from atmospheric sample RO 5 and microlayer water (dissolved and ~~iculate). k Series extending beyond perylene. Ph = phenanthrene; Fl = ~uoranthene; Py = pyrene; Ch = chtysene + t~ph~ykne + ~~~a~anthr~~e; BF = henze(j) + ~~~k)fluoranth~e; BP = benzo(a)pyrcne + ~~de)pyr~e; Pe = perylene.
PAH in Norwqian marine air. Gagosian et a!. (1982) found no indi~id~i PAN con~tration > 5 pgm - 3 in aerosols from the Tropical North Pacific. PAH concentrations that we present for aerosols collected over the Atlantic are much lower than those obtained for continental atmosphere: 6 ng m- 3 for the air collected over a forest from the Ivory Coast (Tissier, 1981) or for particles from urban or suburban areas: near Los Angeles (Gordon, 1976); 5-26ngm-3 OS-l.1 ngmv3 (individual PAH) in air over Great Lakes, U.S.A. (Eisenreich et al., 1981); 30 ng m - 3 in air masses collected over Sweden ori~nating from France and England (Lunde and Bjerseth, 1977); i-52.?ngmv3 inairover Norwayand0.5-92.4ngm-3 in air over Sweden (Ejiirseth et al., 1979); and others (Lao et ul., 1973; 19’75;Dong et al., 1976; Lee et al., 1977; Van Vaeck and Van Cauwenberghe, 1978). From data presented in Table 2, it appears that PAW are essentially (more than 90 %) gaseous in the atmosphere, This fractionation between gaseous and partictdate PAH is about the same as that encountered for n-afkanes, reviewed by Marty (1981) and Duce and Gagosian (1982). The predominance of gaseous PAH in the marine atmosphere was not expected since PAW are introduced into the atmosphere in particulate form (NAS, 1972) and tend to remain associated with particles, in
contrast with PCB’s for which at least 8Op, is transported in gaseous form (Bidleman et al., 1977). Such a ~~orni~n~ of gaseous PAH has been preceedingly noted by Cautreeh and Van Cauwenberghe (1978) for continental atmospheres. They indicated values for the distribution factor between the particulate and the gas phase samples varying from 0.027 for phenanthrene and anthra~~, 0.488 for pyrene up to 11.5 for ~nzo(k)fluoranthene and ~~o~b)fluoranthene. Van Vaeck and Van Cauwenberghe (1978) have collected suburban aerosols, separating particulates as a function of particle size. They have shown that 95 f, of PAH was in the size class =z 3 pm and 60-70 3, was associated with particles c f pm. The data of Pierce and Katz (1975) and Katz and Pierce (1976) indicated that PAN are transported in the atmosphere principally in association with sub-pm particles (those particles which are not eflicientiy scavenged by rain, Lodge er uf., 1981). For ~rine~rosols, a very few data are avaiiable, Ha et al. (1984) have recently shown that the eoncentrationsof PAH as a function of particle size over the Mediterranean Sea was characterized by a maximum for particles _ 1.5 Brn in diameter; but the pyrolytic-iike fractions were associated with smaller size aerosols. Further examination of PAH distributions are necessary to determine the true state of PAH in the marine atmosphere: really gaseous or
Gaseous and particulate
&
Pv
(PAH)
2187
pyrene
f luoranthene
triphenylene
Ch
chryrene
BF
benzo(
j )
6
benro( l() f luoranthene
BP
benzo(
e)pyrene
benzo(a)pyrene
Pe
hydrocarbons
anthracene
phensnt hrene
Ph
FI
polycyclic aromatic
benz (ajanthracen.2
parylcne
Fig. 3. Structures of major
associated with very small-size particles, not retained by glass fibre filters. In order to reach the sampling sites (more than 1000 km from coasts in some cases here), ‘gaseous’ PAH must be less subjected to photo-oxidation than the rate predicted by laboratory models. This hypothesis is not new, as some in vitro experiments have shown that photo-oxidation may be slow for some PAH in the presence of oxygeneted derivatives such as phenols present in the atmosphere, or finally by singlet oxygen capture by complex metallic ions, as discussed by Neff (1979). Distribution and nature of PAH in the atmosphere Gaseous PAH. Distributions of major PAH, gaseous and associated with particles are different as
PAH
and abbreviations used.
shown in Fig. 2, for the representative sample R05 (other samples have respectively exactly the same distributions). Gaseous PAH are mostly constituted by the most volatile compound (phenanthrene). This repartition is consistent with the remarks of Junge (1977) and Marty (1981). They showed that a compound having a vapor pressure value up to lo- 5 mm Hg might be present as gases in the atmosphere. This happens for phenanthrene, whose vapor pressure value is 6.8 x 10W4mm Hg (Handbook of Chemistry and Physics, 1972-73), but not for heavier molecular weight compounds; for example, pyrene (vapor pressure 6.8 x lo- ’ mm Hg). The distribution of alkylated components, as an example in the phenanthrene series (Fig. 4) is dominated by the parent compound and would suggest a
2188
J. C
MART\
PI ui
The distribution of major PAH as well as that of alkylated homologues of phenanthrene (FIN. 4) supgests, as for gaseous PAH. a mixed nature: pyrolyttclike PAH and petroleum-like PAH. These distnbutions cannot be only explained by a partitionlnp ot PAH emitted in the continental atmosphere by man’s activity between gaseous and particulate phases. The analysis of the nature of PAH in surface waters will give further evidence for the ‘oceanic ortgm’ of atmospheric PAH.
R05 Part:culate
Origin of PAH in the atmosphere
/“\ / \
0.5
b
l> I +a 0.51 Microlayer D~esolvcd
Microlayer Particulate
Fig. 4. Distributions of alkylated homologues (Cl -C4) of phenanthrenc (normalized to phenanthrenc) for sample ROS and microlayer water, for dissolved and particulate species.
fossil fuel combustion origin for these PAH. But it is known that petroleum hydrocarbons produce a distribution maximizing at the C3 or C4 alkyl homologue (Wakeham and Farrington, 1980) and if, due to fractionation processes at the sea-air interface (or in the atmosphere), the lighter molecular compounds are favoured during evaporation, we cannot exclude a partly petroleum origin for these compounds. Particulate PAH. Marine aerosols PAH distributions (Fig. 2) exhibit the predominance of phenanthrene, but also the presence of other PAH such as tluoranthene, pyrene, chrysene, benzofluoranthenes and benzopyrenes) at non negligible concentrations. Two main differences can be mentioned, existing between this repartition and those observed for urban and suburban aerosols (i) the absence of perylene, which is not surprising, this compound being of land origin, (Aizenshtat, 1973) and the absence of compounds with molecular weight > 252 and (ii) the relative abundance of phenanthrene. Phenanthrene was not detectable or reported in very low concentrations in urban aerosols by Gordon (1976) and Van Vaeck and Van Cauwenberghe (1978). Bjdrseth et al. (1979) reported large concentrations of phenanthrene, but without predominance over other PAH in the atmosphere over the Atlantic.
In order to determine the possible relationship between PAH from the atmosphere and from sea water, PAH have been analysed in the sea surface microlayer from the same area. As shown in Fig. 2, the distributions of PAH both dissolved and associated with particles are different. Low molecular weight PAH (phenanthrene and fluoranthene) predominate in the dissolved fraction. This could be explained by the higher solubility of these compounds with respect to higher molecular weight PAH. The preferential solubility explains also the distribution of alkylated homologues of phenanthrene in the dissolved fraction (Fig. 4). On the other hand, the particulate PAH distribution (Fig. 2) and the distribution of alkylated homologues maximizing at C3-C4 species suggest strongly a noncombusted petroleum-type material (Wakeham and Farrington, 1980). From this type of petroleum residue which is common in most of oceanic areas (Burns and Villeneuve, 1983), evaporation would lead to a relative increase of components having the highest vapor pressure values: phenanthrene and its alkylated derivatives, fluoranthene. Thus, two origins can be proposed for gaseous PAH identified in the open ocean atmosphere (i) evaporation of particulate pyrolytic-like PAH emitted into the atmosphere over continents and (ii) evaporation of pyrolytic-like or non-combusted petroleum accumulated at the sea-air interface. In the two cases the modification of PAH characteristics by physicochemical processes in the water phase such as preferential solubilization of light compounds and nonalkylated derivatives, may assist in the repartition of PAH observed both in sea water (dissolved phase) and aerosols. The origin of PAH in the particulate form is more difficult to define. The resemblance between particulate PAH from the atmosphere and dissolved PAH from the sea surface microlayer suggests that PAH from aerosols are probably emitted from the sea by bubble bursting process, which introduces droplets of sea water into the atmosphere. We cannot totally rule out the hypothesis of a direct input to the marine atmosphere of terrestrial dusts (like those analysed by Laflamme and Hites, 1978), whose PC-H distributions would be very close to that of atmosphere samples we have analysed, in agreement with previous observations by Simoneit and Eglinton (1977) who indicated
Gaseous and particulate polycyclic aromatic hydrocarbons (PAH)
the presence of lipid molecules typical of continental soils in dusts collected in the same oceanic area as our samples. Nevertheless, the analyses presented in Figs 2 and 4 strongly suggest that both unburned petroleum PAH accumulated in the sea surface microlayer essentially as particulates and pyrolytic-like compounds fractionated in the ocean according to their solubilities, are emitted into the atmosphere faster than continental dusts are deposited. A separation of aerosols as a function of particle size such as realised recently by H6 et al. (1984) and the systematic collection of dusts would be useful to differentiate between the net fluxes of both pyrolytic-like petroleum-derived PAH at the sea-air interface.
and
Acknowledgements-We are grateful to Dr. K. Bums for helpful comments on the manuscript.
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