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ENVIRONMENTAL

POLLUTION

ELSEVIER Environmental Pollution 99 (1998) 29-36

Polycyclic aromatic hydrocarbon (PAH) dispersion and deposition


to vegetation and soil following a large scale chemical fire
A.A. Meharg, J. Wright, H. Dyke, D. Osborn
Institute of Terrestrial Ecology, Monks Wood, Abbots Ripton, Huntingdon, Cambridgeshire PE17 2LS, UK

Received 25 June 1997; accepted 29 October 1997

Abstract

Polycyclic aromatic hydrocarbons (PAHs) were determined in soil and vegetation following a large scale chemical fire involving
10 000 ton of polypropylene. In comparison with sites outside the plume from the fire, PAH concentrations were elevated in grass
shoots (by up to 70-fold) and in soil (by up to 370-fold). The pattern of PAH dispersion under the plume was dependent on the
physical-chemical properties of individual PAHs. The lighter, least hydrophobic PAHs were dispersed into the environment at
greater distances than heavier, more hydrophobic PAHs. At the most distant sampling point (4.5 km) under the plume, the low
molecular weight PAHs were still considerably elevated in vegetation samples compared to control sites. Dispersion appeared to be
regulated by the compounds partitioning between the vapour and particulate phase, with dry particulate deposition occurring closer
to the fire source than gaseous deposition. For all PAHs, the fire resulted in greater contamination of soils compared to grasses,
with the relative ratio of plant/soil contamination decreasing as hydrophobicity increased. © 1998 Elsevier Science Ltd. All rights
reserved.
Keywords." Chemical accident; Grass; PAHs; Plastics fire; Pollutant deposition; Soil

I. Introduction dependence on physical-chemical properties with


respect to their affinities for gas phase and dry particu-
Fires involving organic chemicals can produce com- late phase (Harrison and Jones, 1995; Tremolada et al.,
plex cocktails of semi-volatile organic pollutants, 1996). In the absence of precipitation, chemical fallout
including polycyclic aromatic hydrocarbons (PAHs) from smoke plumes will be as dry-gas deposition or as
(Mitera and Michal, 1985; Levin, 1987; Wheatley et al., dry-particulate deposition. For terrestrial ecosystems,
1993) and dioxins and furans (Meharg and Osborn, vegetation and soil will be the initial receptors for both
1995; Meharg et al., 1997). The potential for pollutant particulate and gaseous atmospheric pollutants (Simo-
dispersion and deposition from smoke plumes generated nich and Hites, 1994, 1995). Soil and plant shoot con-
by massive fires may be considerable (Ghoniem et al., tamination from atmospheric deposition is the major
1993; Meharg and Osborn, 1995). Dispersion of pollu- route of entry of semi-volatile compounds released by
tants generated by chemical fires will be complex, prin- accidents into agricultural and wildlife food chains
cipally as the large range of physical-chemical (Meharg et al., 1997).
properties of individual pollutants within smoke-plume PAHs are common pollutants produced by a wide
mixtures will result in differential spatial and temporal variety of combustion sources, including the incomplete
distributions of these contaminants within the receiving combustion and pyrolysis of a wide range of plastics
environment (Meharg and French, 1995). This com- (Levin, 1987), including polypropylene (Mitera and
plexity is exacerbated as pyrolysis and combustion con- Michal, 1985; Fardell et al., 1986; Wheatley et al., 1993).
ditions will vary throughout the course of fires, leading An opportunity arose to investigate the factors regulat-
to temporal fluctuations in pollutant production ing environmental distribution of PAHs following a
(Meharg, 1994). massive chemical fire involving 10000ton of poly-
Atmospheric monitoring for background and point propylene. Both grass shoots and soils were analysed for
source levels of semi-volatile organics all show strong 16 PAHs (the standard World Health Organisation

0269-7491/98/$19.00 © 1998 Elsevier Science Ltd. All rights reserved.


PII: S0269-7491 (97)00180-2
30 A.A. Meharg et al./Environmental Pollution 99 (1998) 29-36

P A H base set; U S D H H S , 1995,a b) along a transect


bisecting the smoke plume. Spatial P A H deposition,
and the ratio of vegetation/soil contamination were
modelled using physical-chemical descriptors.

2. Materials and methods

2.1. Accident description

The fire started in a warehouse on the 9/10/95 at


05.35 h and was extinguished by 14.40 h. The warehouse
was used to store 10 000 ton of polypropylene in pelleted
form for moulding. Following the incident, information
on plume direction and width, and the wind speed
throughout the fire was obtained from the U K Meteor-
ological Office's Chemnet service (Bennett and Weston,
1989).
Surface wind speed from 08.40--11.40h at 180 ° was
2 8 k m h -1 with gusts up to 3 8 k m h - 1 ; average mixed
layer wind speed was 3 5 k m h - l from 200 °, air tem-
perature was 15°C rising to 19°C, humidity 85%, pre-
cipitation nil and depth of mixed layer was 1 500 m. The
surface wind speed from 11.40-14.40h at 190 ° was
30 km h -1 with gusts up to 40 km h -l, slowly decreasing
to 2 0 k m h -1 with gusts to 3 0 k m h -1. Average mixed
layer wind speed was 4 0 k m h -I from 210 ° gradually
decreasing to 3 5 k m h -1. Air temperature was 19°C ris-
ing to 22°C, precipitation nil and depth of mixed layer
was 15 000 m.
Vertical dispersion of the plume was slow, while hor-
izontal dispersion was moderate to occasionally rapid, Fig. 1. Plume dispersion during the polypropylenefire. The dot-dash
throughout the entire time course of the fire. The plume line shading indicates plume dispersion from 05.30-11.40h while the
dispersion modelled by Chemnet was entered into a dashed line indicates dispersion from 11.40-14.40h. Samplingsites are
numbered and marked with triangles while the site of the warehouse is
Geographical Information System. Plume direction was
marked with a solid square.
plotted in Fig. 1 for the two time periods, 05.35-08.40 h
and 11.40-14.40 h.
30 mm diameter corer was used to obtain soil cores. The
2.2. Sampling corer was thoroughly washed in distilled water and
dried after each sample was taken. Three replicate grass
Environmental samples were collected 48 h after the and soil samples were obtained at each site, collected
incident. There were no precipitation events between the along a transect at 10m spacing. Soil and grass samples
start of the fire and sampling termination. Soil and were collected in glass Kilner jars.
vegetation samples were collected at distances
2.5-4.6km under the plume from the warehouse and 2.3. Sample preparation
1-2.2km in the opposite direction to the plume (180 °)
(Fig. 1). Samples were not collected closer to the site of Samples were returned to the laboratory on the day
the accident as there was no access to the industrial of sampling where sub-samples of both soils and vege-
complex in which the warehouse was located. The most tation were immediately extracted with dichlor-
distant sampling point under the plume was on the omethane (DCM) in preparation for PAH analysis.
coast line (Fig. 1). The plume was observed to be carried Approximately 40 g of soil was weighed into a 250 ml
still further out over the sea. Sampling site descriptions glass bottle fitted with a Teflon lined screw top. The soil
are given in Table 1. Inputs to the sea surface were not was dried by stirring in 20 g of anhydrous sodium sul-
determined. phate. H P L C grade D C M (50ml) supplied by Rath-
Soil (to a depth of 10cm) and grass shoots from burns, U K was added to the soil and the contents of the
rough grassland were collected at all sampling points. A bottle were mixed by shaking and inversion. The
A.A. Meharg et al./Environmental Pollution 99 (1998) 29-36 31

Table 1
Site and soil descriptions for sampling points shown in Fig. 1
Sampling site Distance from warehouse Site description Soil type
(kin)
1 1.0 rough grassland boulder clay
2 1.9 rough grassland boulder clay
3 1.6 rough grassland boulder clay
4 2.4 tilled silty clay
5 2.5 tilled silty clay
6 3.0 wasteland silty clay
7 3.2 wasteland impacted clay
8 4.0 fixed dune sand
9 4.5 dune sand

samples were left overnight before continuing the Sub-samples of soil and vegetation samples were
extraction procedure. The soil was then extracted dried at 70°C to a constant weight and this information
another 4 times with 50ml aliquots of DCM. Sample was used to report PAH data on a dry weight basis.
blanks consisted of empty Kilner jars taken out and
opened in the field. Subsequent extraction and sample 2.4. P A H analysis
treatment of blanks was identical to the extraction pro-
cedures outlined above. There was one blank for soils The GC-MS model was a Hewlett Packard (UK)
and one blank for vegetation. 5890 gas chromatograph interfaced to a 5972 mass
Approximately 20 g of vegetation were weighed into a selective detector. An autosampler was used to inject
500ml Kilner jar to which 100ml of D C M (HPLC 5 #1 of sample. The injection technique was split/split-
grade) was added and the contents of the jar were mixed less at 250°C. The column was a 3 0 m × 0 . 2 5 m m id HP5
by swirling. The samples were left overnight before MS fitted with a 5 m × 0 . 2 5 m m id deactivated retention
continuing the extraction procedure. The vegetation was gap. The carrier gas was helium held at 1.75mlmin -I
then extracted by the same extraction procedure a fur- throughout the run by electronic pressure control. The
ther 4 times. column oven was held at 40°C for 2min and then
Both the soil and grass DCM extracts were trans- ramped at 10°Cmin -1 to 300°C. The mass spectrometer
ferred to a 500ml Kuderna-danish flask via a funnel was run in select ion mode. The 3 most abundant ions
containing 10g of anhydrous sodium sulphate. The were monitored for each compound except for naph-
extract in the Kuderna-danish flask was reduced to thalene where only 2 ions were monitored. The PAHs
2.5ml in a water bath at 55°C. The volume of the determined are reported in Table 2.
extract was reduced to exactly 2ml using a stream of The identity of a chromatographic peak was identi-
electron capture grade nitrogen (British Oxygen Com- fied by comparison of the peak's relative retention time
pany, UK). with the relative retention times of peaks in the stan-
Clean-up was carried out by alumina column chro- dard. This operation was performed automatically by
matography. The alumina was prepared by decontami- the GC-MS chromatography data system and chroma-
nation in a muffle furnace at 700°C for 4 h followed by tograms were checked manually by overlaying the stan-
deactivation with the addition of 5% water (w/w). The dard and sample chromatograms. Retention time of the
alumina column consisted of 3.5g of deactivated alu- internal standard was used to correct for variation in
mina packed into a 7 mm diameter glass column. retention time. Comparison of the ion ratios of the rele-
Extract (200 #l) was placed on the column and the vant standard peak with the ion ratios of the unknown
PAHs eluted with 5ml of hexane. The eluant was in the sample were used as confirmation of peak iden-
reduced to 0.5 ml under a stream of nitrogen. An inter- tity. The peak area of the most abundant of the three
nal standard of 2,6-dichlorobenzonitrile was added to ions monitored (target ion) was used for all quantitative
the samples to give a final concentration 0.5/zgm1-1. calculations.
Recovery and blank samples were included with each
batch of soil and vegetation samples. Material used to
calculate recoveries was soil and vegetation from a rural 3. Results and discussion
site. This material was spiked with a P A H mixture and
extracted identically to the samples. Unspiked samples Levels of 16 PAHs in soils and vegetation at the dif-
of the material used to calculate recoveries were also ferent sampling points were determined and related to
analysed to subtract background levels from the spiked the plume distribution plot (Fig. 1). The graphs illus-
material. Recoveries were run with every 15 samples. trating the PAH distribution (Fig. 2) are ranked in
32 A.A. Meharg et al./Environmental Pollution 99 (1998) 29-36

Table 2 the higher the Kow, the greater the PAH association
Log octanol-water partitioning coefficients (Kow) and Henry's law with the atmospheric particulate phase compared to the
constants (H) for the P A H s analysed following the accident. Physical-
vapour phase (Harrison and Jones, 1995). This pattern
chemical parameters were obtained from US Dept Health H u m a n
Services U S D H H S (1995a, b)
of partitioning of PAHs between vapour and particulate
phase has also been observed for PAHs generated dur-
PAH log Kow Vapour pressure H ing chemical fires (Atlas et al., 1985). Results of this
(kPa) (atm m 3 m o l - i)
study support the hypothesis that increasing Kow shifts
Naphthalene 3.29 0.012 4.60x 10 -4 vegetation burdens arising from the vapour phase par-
Acenaphthene 3.98 5.81 × 10-4 3.98 x 10-3 titioning to particulate dry deposition. This theory
Acenaphthylene 4.07 0.004 1.45x 10 -3 explains the dependency of the vegetation contamina-
Fluorene 4.18 4.16×10 -5 1.00x 10-4
Anthracene 4.45 2.26× 10 -6 1.77x 10 -5
tion pattern on Kow. A study investigating PAH
Phenanthrene 4.45 9.04× 10-5 2.56x 10-5 deposition to azalea leaves (Nakajima et al., 1995)
Pyrene 4.88 3.33×10 -7 4.88x10 -5 supports this hypothesis as partitioning of less
Fluoranthene 4.90 6.66x 10 -7 6.30x 10 -6 hydrophobic PAHs onto plant surfaces was through
Chrysene 5.16 8.38x10 - s 1.05x 10-6 gaseous dry deposition, whilst particulate deposition
Benzo(a)anthracene 5.61 2.93 × 10 -9 1.00x 10 -6
Benzo(b)fluoranthrene 6.04 6.66x 10- s 1.22x 10-5
dominated contamination for the more hydrophobic
Benzo(k)fluoranthrene 6.06 7.86x 10-12 3.87× 10 -5 compounds.
Benzo(a)pyrene 6.06 7.45x 10 - l ° 4.90x 10 -7 Examining the deposition pattern for the compounds
Benzo(g,h,i)perylene 6.50 1.39×10 -I1 1.44x 10-7 with the highest Kow indeno(l,2,3-c,d)pyrene and
Indeno(l,2,3-c,d)pyrene 6.58 1.33 x 10 -12 6.90x 10 -8 dibenzo(a,h)anthracene, the sampling regime is giving
Dibenzo(a,h)anthracene 6.84 1.33 × 10-N 7.30x 10- s
incomplete information as to the distribution of PAHs.
The sampling transect effectively cuts through the plume
at an angle, with points 4 and 5 falling outside the
plume, while 6-9 were directly under the plume (Fig. 1).
order of increasing log octanol-water partitioning coef- As concentrations for indeno(1,2,3-c,d)pyrene and
ficient (Kow) Kow values are given in Table 2. dibenzo(a,h)anthracene were maximum at point 6, the
first point directly under the plume, this is suggestive of
3.1. P A H levels in vegetation the fact that deposition was also occurring closer to the
fire source directly under the plume. However, the
The distribution of PAHs in grass shoots along the graphical display does show the substantial elevation in
plume transect was highly dependent on the com- concentrations at this point compared to vegetation
pound's Kow. The least hydrophobic compounds, outside the plume, and it also clearly shows the marked
naphthalene-phenanthrene (Table 2), had the same decline in levels at sampling points directly under the
pattern of distribution. Levels at sites 4, 5 and 6 were at plume further away from the source. For all other PAs,
background, while there was a steep rise (about 10-fold) vegetation burdens were low at site 6 which was directly
at sampling point 7, 3.2 km from the fire source. These under the plume, and rose sharply at point 7. This
high levels were maintained at all subsequent sampling pattern strongly suggests that gaseous PAH vapours
points. Site 6 at 3 km was directly under the plume yet arising from the fire were not grounding in substantial
had background levels of contamination. Compounds quantities until a distance of 3.2 km from the fire.
with Kow of 4.9--6.5 (Table 2) differed in their distribu- Elevation of PAHs above control values for grasses
tion compared to the lighter PAHs, but tended to have ranged from 9-67 fold for this study's maximum
similar distributions to each other, again with a sharp concentrations (Fig. 2). The background levels of con-
rise in concentrations at 3.2 km, but decreasing again at tamination at the control sites are within the ranges
sampling point 8 at 4 kin, tailing off to background at published for rural (Jones et al., 1992; Wild et al., 1992)
sampling point 9. The 2 most hydrophobie compounds, and urban (Yang et al., 1991) grasses. Yang et al. (1991)
indeno(1,2,3-c,d)pyrene and dibenzo(a,h)anthracene, recorded Y~PAH levels in grasses 0.5 m from an urban
showed a different contamination pattern, with the roadside of 90 ng g- 1 compared to the 153 ( + 8.2) ng g-i
highest levels determined at sampling point 6 (3 km) and recorded in the control sites (1-3) reported in this study.
tailing off to background levels at subsequent sampling Jones et al. (1992) reported values of 187ngg -l for
sites. rural grass samples collected between 1985-1989. The
The shift towards deposition of PAHs closer to the control sites recorded in the present study (sites 1-3),
fire source as the Kow increases suggests that the more sites 4 and 5 on the edge of the plume and the sites
hydrophobic compounds were being deposited via par- under the plume (sites 6-9) are all on the edge of a
ticulates, while with decreasing hydrophobicity, shoot major industrial complex, situated on the border
contamination appeared to regulated by partitioning between the city and countryside. Prevailing winds were
of vapour phase PAHs onto leaf surfaces. In general, from the sea (easterlies). Therefore, strict classification of
A.A. Meharg et al./Environmental Pollution 99 (1998) 29-36 33

laphthalene chrysene
490 115 2000 ~ 300
368 86 1500 t 225
245 58 1000 150
123 29 500 ~_ 75
0 0 0 - 0
acenaphthene fenz°(a)anthr~[
36 100 1400 180
27 75 1050
18 50 700
9 25 350
0 O0 0 .... 0
acenaphthylene ~enzo(b)fluoranthene
105 36 2000 240
79 27 1500 180
53 18 1000 120
A
25 9 500 60 "0
0 0 0 . . . . . . . . . . . O
luorene ~enzo(k)fluoranthene "0
'01 125 40 12oo 140
O~
4- 94 30 900 105 o
n
63 20 600 70
C
_o 31 10 300 35 =~
! 0
mthracene / ~ /. ~ ~
0 0 . . . . . .
benzo(a)pyrene ,
0

ut - 120 20 1200 -~. 80 =


O 90 15 900 60
0
60 10 600 40
~o,. 3o 5 300 20 -
o 0 0 0 ~z
o ~henanthrene ~enzo(g,h,i)pe/~.e ~-. l :~
16oo 360 300 t 6.0
1200 "~ 270 225 i 45
800 180
400 9O 75 ! 1.5
o 0 0 I 0.0
650 ndeno(1,2,3-~)pyrene ........ t 10.0
2600 ~ 420
1950 315
1300 210 325 5.0
650 105 163 2.5
0 - 0 0 ~ O0
luoranthene
2600 ~ j 440 2400120018006i00Ji0benzo(a,h)a
~ hracene iL 9362718
- 4 0}!~
1950 330
1300 220
650 110
0 0
20 2.5 30 35 40 45 50 20 25 30 35 40 45 50
distance (km) distance (km)

Fig. 2. Plots of shoot (triangles and dashed line) and soil (circles and solid lines) for PAHs along the sampling transect illustrated in Fig. 1. Closed
symbols are for samples under the plume and open symbols for controls collected at 180° to the direction of the plume. Each point is the average of
3 replicate determinations ± the standard error of the mean. Plant and soil levels were scaled so that maximum concentration for each PAH
appeared at the same position on the y-axis.

these sites as urban, suburban and rural is not possible potential point sources (Fig. 2), indicating that the
given the local demography and weather patterns. accident was responsible for the considerable elevation
It was possible that other point sources of PAH pol- in soil levels at sites 6 and 7 and in vegetation at sites 6-9.
lution contributed considerably to soil and vegetation The ZPAH recorded for vegetation at the most con-
burdens. Such point sources could have included the taminated site (2365ngg -1) exceeds any literature
nearby steel works, chemical plants and roads (Fig. 1). reports of background levels of PAHs in grasses, though
However, as these sources have been in existence for levels in other vegetation types from urban/suburban
considerable lengths of time, if they were continuous areas are at or about the levels recorded in this study. A
sources of PAHs there should be greater elevation in study on urban/suburban maple (Wagrowski and Hites,
soil burdens at sampling sites near these installations 1997) and pine (Tremolada et al., 1996) recorded/zg -1
compared to more remote sampling points. This is not levels of EPAHs in leaves and needles. However, the
the case at sites 1-3 and 8 and 9 which were all near cuticular wax content, particularly for pine, is much
34 A.A. Meharg et al./Environrnental Pollution 99 (1998) 29-36

higher than for grasses and, therefore, comparisons 0.6-


between grass and tree leaves may be misleading. vapour pressure
0.5- o
0.4- o
3.2. P A H levels in soil
0.3.

0.2"
In contrast to vegetation, PAH levels in soil all had
0.1
the same general deposition pattern, with the sole
exception of naphthalene (Fig. 2), the compound with 0.0
-1 -2 -3 -4 -5 -6 -7 -8 -9 -10 -11 -12 -13
the lowest Kow (Table 2). The general pattern for PAH log vapour pressure (kPa at 25°C)
contamination was that the highest levels were at site 6, 0.6"
-I octanol-water partition coefficienl
the site closest to the source that was directly under the O 0.5. o
131)
plume. Again, this contamination pattern suggests that - ~ 0.4. o
PAHs may have been elevated closer to the source. J~ 0 . 3
O~ o
Access to such sites was restricted so this remains a (~ 0 . 2
hypothesis. Contamination decreased from site 6 to site o
tO 0.1
7 for all PAHs, excluding naphthalene, but were still at 11)
~O 0.0
levels considerably elevated above background. Levels 4 5 6
between site 7 and site 9 showed a linear decline, with U
log Kow
levels at site 9 for all PAHs being at background (Fig. 2). "1- 0.6
< Henry's law constant
Naphthalene differed from all the other PAHs in that Q.. 0.5 o
maximum deposition did not occur until site 7 rather "~ 0.4 o
than site 6 (Fig. 2), though the levels at site 6 were still ~ 13.3
elevated. The decrease in PAH levels between sites 7 and
o ~ o
Q- 0.2
9 observed for the other PAHs was also observed for O
~ 0.1
naphthalene. 0.0
Elevation of PAHs in soils under the fire plume at -6 -7 -6 -5 -4 -3 -2
maximum concentrations above background levels ran- log H (atm-m 3 tool ~)
ged from 17-fold to 366-fold (Fig. 2). Background levels 0.6 multiple regression
of EPAHs in the soil determined during this study o.s 0
(average of sites 1-3) were 2697+537ngg -1. This is 0.4 0

within the range of EPAHs recorded in soils from simi- 0.3 .......-@''~O 0
lar industrial environments; chemical plants and steel 0.2 ~ 0
works (Weiss et al., 1994), aluminium plant (Wilcke et 0.1
al., 1996) and urban conurbations (Butler et al., 1984). o.o p ~-' ' 1 0
However, the most contaminated soils in the present -1.6 -1.2 =0.8 -0.4

study had PAH levels (12-18mg kg -1) that were also x--- 0.55 -0.25*lOgKow + 0.015*logvp + 0.029*logH
within the range of soils from highly industrialised areas Fig. 3. Regression of physical-chemicalproperties of PAHs against
(Weiss et al., 1994) and from soils collected 1 m from a the ratio of plant-soil concentrationof the maximumcontamination
very busy motorway (Butler et al., 1984). Therefore, the observed for each matrix (independentof samplingpoint), designated
most contaminated soils determined in this study are maximumcontamination-backgroundcontamination(averageof sites
1-3). Physical-chemicalparameters were obtained from US Dept
not exceptional when compared to other industrial and
Health Human ServicesUSDHHS (1995a, b). Multipleregressionwas
urban environments. carried out using Minitab (v. 11) usingstepwiseregression).

3.3. Comparison o f P A H burdens in vegetation and soil

For all compounds, with the exception of for the soils and vapour partitioning for the plants.
indeno(1,2,3-c,d)pyrene and dibenzo(a,h)anthracene, The deposition pattern was very similar for all PAHs in
the distribution patterns in soils and plants were not soils, whilst it was dependent on physical-chemical
synchronised, with maximum soil concentrations properties for plants (Fig. 2). That is, that the bulk
occurring at site 6 and maximum plant concentrations of soil contamination was from dry deposition of par-
at sites 7-9. The least hydrophobic PAH (Kow ranging ticulates, whilst the bulk of vegetation contamination
from 3.3-4.45) levels in plant shoots remain elevated at was from vapour phase partitioning for the lighter
an increasing distance from the fire source, whilst those PAHs.
in soil always declined from the maximum value at site It is possible that soil contamination resulted from
6. This suggests that 2 mechanisms of contamination both dry particulate contamination and from vapour
were occurring, principally dry-particulate deposition partitioning of gaseous PAHs, but comparing the
A.A. Meharg et al./Environmental Pollution 99 (1998) 29-36 35
vegetation and soils data (Fig. 2), it appears that one 4. Conclusions
mechanism dominates for soils and the other for veget-
ation, with the exception of indeno(1,2,3-c,d)pyrene and It has long been recognised that pyrolysis and com-
dibenzo(a,h)anthracene, where the distribution pattern bustion of plastics, including polypropylene, may result
along the transect was identical for plants and soils. in considerable production of PAHs (Mitera and
For compounds with intermediate Kow (4.9-6.5), the Michal, 1985; Levin, 1987; Wheatley et al., 1993).
soil and vegetation pattern became more similar, However, it had not been previously demonstrated that
although out of synchrony at sites 6 and 7. The pattern large scale plastics fires could result in considerable
of contamination for indeno(1,2,3-c,d)pyrene and environmental pollution of receiving habitats with
dibenzo(a,h)anthracene, the most hydrophobic of the PAHs. The results of this study show that vegetation
PAHs analysed, in soil and vegetation was virtually burdens were elevated up to 70-fold and soil burdens up
identical (Fig. 2). As the soil contamination pattern for to 370-fold for some PAH compounds. In addition,
PAHs was similar for all compounds (except naphtha- particulate deposition of PAHs was occurring closer to
lene), this again argues that soil contamination is domi- the fire source for all PAHs compared to vapour phase
nated by dry-particulate deposition. That the vegetation dispersion. PAHs found predominantly in the vapour
pattern follows the soil contamination so closely for the phase were still highly elevated in vegetation up to
2 most hydrophobic PAH compounds also suggests that 4.5 km from the fire source.
shoot burdens were also dominated by dry-particulate Other studies on the environmental pollution result-
deposition for these two compounds. If this is the case, ing from chemical fires show that pollutants may be
then a component of shoot contamination is through dispersed into the environment at distances in excess of
dry-particulate deposition, with this becoming more 1 km from the fire source (Marklund et al., 1989; Pha-
dominant at higher Ko,~s. neuf et al., 1995). However, other large scale fire inci-
Vegetation PAH burdens range from ~40% to 1.5% dents resulted in major deposition only occurring close
of the levels found in soils, when the most contaminated to the fire base (Meharg and French, 1995). Dispersion
samples for each PAH were compared, with the fraction of pollutants from chemical fires will be highly depen-
decreasing with increasing Kow (Fig. 3). Vapour pres- dent on prevailing weather conditions on the buoyancy
sure and Henry's law constant also correlated well with of the smoke plume (Ghoniem et al., 1993), and the
the relative quantities of PAHs in plant shoots and in nature of source materials and fire temperatures
soils (Fig. 3). This again suggests that as Kow increased (Meharg, 1994). The observation that PAHs distributed
and vapour pressure decreased (Kow and vapour pres- over kilometre distances can behave according to their
sure are negatively correlated), the contribution of gas physical-chemical properties is a useful finding in a field
phase partitioning to shoot PAH burden increased. It normally dominated by high degrees of variation.
also suggests that vegetation only intercepted a small
fraction of the dry particulates resulting from this acci-
dent. As environmental material was sampled only
2 days after the accident, there may have been loss of Acknowledgements
PAHs from plant leaves (and from soils) through re-
volatilisation back into the atmosphere. This process We wish to thank the UK Department of the Envir-
would be dependent on the PAHs physical-chemical onment who funded this study under contract EPG 1/5/
properties, with more volatile, less hydrophobic 55. The views expressed in this study do not necessarily
compounds being lost at a more rapid rate. Thus the reflect those of the Department.
slope of the regression for ratio of vegetation/soil con-
tamination plotted against PAH physical--chemical
properties may have been more steep at time intervals
during and immediately after the incident as predicted References
from clearance rates of removal of semi-volatile organ-
ics adsorbed onto leaf surfaces from the gas phase (see Atlas, E.L., Donnelly, K.C., Giam, C.S., McFarland, A.R., 1985.
Chemical and biologicalcharacterisation of emissions from a fire-
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