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PAHs Pollution

PAHs Pollution

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E L S E V IE R
E n v iro n m e n ta l P o llu tio n 9 9 (1 9 9 8 ) 2 9 -3 6
E N V IR O N M E N T A L
P O L L U T IO N
P o ly c y c lic a r o m a tic h y d r o c a r b o n
(PA H ) dispersion and deposition
to v e g e ta tio n
a n d s o il fo llo w in g a la r g e s c a le c h e m ic a l fir e
A .A . M eharg, J. W right, H . D yk e, D . O sborn
In s titu te o f T e r r e s tr ia l E c o lo g y , M o n k s W o o d , A b b o ts R ip to n , H u n tin g d o n , C a m b r id g e s h ir e P E 1 7 2 L S , U K
R e c e iv e d 2 5 J u n e
1997; accepted 29 O ctober 1997
A b stract

P o ly c y c lic a ro m a tic h y d ro c a rb o n s (P A H s ) w e re d e te rm in e d in s o il a n d v e g e ta tio n fo llo w in g a la rg e s c a le c h e m ic a l fire in v o lv in g 10 000 to n o f p o ly p ro p y le n e . In c o m p a riso n w ith site s o u tsid e th e p lu m e fro m th e fire , P A H c o n c e n tra tio n s w e re e le v a te d in g ra ss sh o o ts (b y u p to 7 0 -fo ld ) a n d in s o il (b y u p to 3 7 0 -fo ld ). T h e p a tte rn o f P A H d isp e rsio n u n d e r th e p lu m e w a s d e p e n d e n t o n th e p h y s ic a l-c h e m ic a l p ro p e rtie s o f in d iv id u a l P A H s . T h e lig h te r, le a s t h y d ro p h o b ic P A H s w e r e d is p e rs e d in to th e e n v iro n m e n t a t g re a te r d is ta n c e s th a n h e a v ie r, m o re h y d ro p h o b ic P A H s . A t th e m o s t d is ta n t s a m p lin g p o in t (4 .5 k m ) u n d e r th e p lu m e , th e lo w m o le c u la r w e ig h t P A H s w e re s till c o n s id e ra b ly e le v a te d in v e g e ta tio n s a m p le s c o m p a re d to c o n tro l site s. D is p e rs io n a p p e a re d to b e re g u la te d b y th e c o m p o u n d s p a rtitio n in g b e tw e e n th e v a p o u r a n d p a rtic u la te p h a s e , w ith d r y p a rtic u la te d e p o s itio n o c c u rrin g c lo se r to th e fire so u rc e th a n g a se o u s d e p o sitio n . F o r a ll P A H s , th e fire re su lte d in g re a te r c o n ta m in a tio n o f so ils c o m p a re d to g ra sse s, w ith th e re la tiv e ra tio o f p la n t/s o il c o n ta m in a tio n d e c re a s in g a s h y d ro p h o b ic ity in c re a s e d . \u00a9

1 9 9 8 E ls e v ie r S c ie n c e L td . A ll rig h ts
re s e rv e d .
K e y w o r d s ." C h e m ic a l a c c id e n t; G ra s s ; P A H s ; P la s tic s fire ; P o llu ta n t d e p o s itio n ; S o il
I .
I n tr o d u c tio n
F ire s in v o lv in g o rg a n ic c h e m ic a ls c a n
produce com -
p le x
c o c k ta ils
o f
sem i-v o latile
o rg a n ic
p o llu ta n ts ,
in c lu d in g
p o ly c y c lic
arom atic
h y d r o c a r b o n s
(P A H s)
(M ite ra a n d M ic h a l, 1 9 8 5 ; L e v in , 1 9 8 7 ; W h e a tle y e t a l.,
1993) and
d io x in s
a n d
fu ra n s
(M eharg
a n d

O sb o rn , 1 9 9 5 ; M e h a rg e t a l., 1 9 9 7 ). T h e p o te n tia l fo r p o llu ta n t d isp e rsio n a n d d e p o sitio n fro m

sm oke plum es generated
b y m a ssiv e fire s m a y b e c o n s id e ra b le (G h o n ie m
e t a l.,
1993; M eharg and
O sb o rn ,
1995). D ispersion

o f p o llu - ta n ts g e n e r a te d b y c h e m ic a l fire s w ill b e c o m p le x , p rin - c ip a lly

a s
th e
la rg e
r a n g e
o f
p h y s ic a l-c h e m ic a l
p ro p e rtie s o f in d iv id u a l p o llu ta n ts w ith in s m o k e -p lu m e
m ix tu re s w ill re su lt in d iffe re n tia l s p a tia l a n d
te m p o ra l
d is trib u tio n s o f th e se c o n ta m in a n ts w ith in th e re c e iv in g
environm ent (M eharg
a n d
F r e n c h ,
1 9 9 5 ). T h is

com - p le x ity is e x a c e rb a te d a s p y ro ly s is a n d c o m b u s tio n c o n - d itio n s w ill v a ry th r o u g h o u t th e c o u rs e o f fire s, le a d in g t o

te m p o ra l
flu c tu a tio n s
i n
p o llu ta n t
p ro d u c tio n
(M eharg, 1994).
A tm o sp h e ric m o n ito rin g fo r b a c k g ro u n d
a n d
p o in t
so u rc e
levels of sem i-volatile organics all show
stro n g
0 2 6 9 -7 4 9 1 /9 8 /$ 1 9 .0 0 \u00a9
1998 Elsevier Science Ltd. A ll rights reserved.
P II:
S0269-7491 (97)00180-2
d e p e n d e n c e
o n
p h y s ic a l-c h e m ic a l
p ro p e rtie s
w ith

respect to their affinities for gas phase and dry particu- late phase (H arrison and Jones, 1995; Trem olada et al., 1 9 9 6 ). In th e a b se n c e o f p re c ip ita tio n , c h e m ic a l fa llo u t fro m

sm oke plum es w ill be as dry-gas deposition or as
d ry -p a rtic u la te
d e p o s itio n .
F o r
t e r r e s t r i a l
ecosystem s,
v e g e ta tio n a n d so il w ill b e th e in itia l re c e p to rs fo r b o th
p a rtic u la te a n d
g a se o u s a tm o s p h e ric p o llu ta n ts (S im o -
n ic h a n d
H ite s , 1 9 9 4 , 1 9 9 5 ). S o il a n d p la n t s h o o t c o n -
ta m in a tio n
fro m
a tm o sp h e ric
d e p o s itio n
is the
m a jo r
ro u te
o f e n tr y o f se m i-v o la tile c o m p o u n d s re le a se d b y
a c c id e n ts
in to
a g ric u ltu ra l
a n d
w ild life
fo o d
c h a in s
( M e h a r g e t a l., 1 9 9 7 ).
P A H s
a re
com m on
p o llu ta n ts p ro d u c e d
b y
a

w id e v a rie ty o f c o m b u s tio n so u rc e s, in c lu d in g th e in c o m p le te c o m b u s tio n

a n d
pyrolysis of a
w id e ra n g e
o f plastics
(L e v in ,
1 9 8 7 ), in c lu d in g
p o ly p ro p y le n e
(M itera
a n d

M ic h a l, 1 9 8 5 ; F a r d e ll e t a l., 1 9 8 6 ; W h e a tle y e t a l., 1 9 9 3 ). A n o p p o rtu n ity a ro se to in v e stig a te th e fa c to rs re g u la t- in g

e n v iro n m e n ta l d is trib u tio n
of PAHs
fo llo w in g
a
m assive
c h e m ic a l
f i r e
in v o lv in g
10 0 0 0 to n
o f

p o ly - p ro p y le n e . B o th g ra ss s h o o ts a n d so ils w e re a n a ly s e d fo r 1 6

P A H s
(th e
s ta n d a r d
W o rld
H e a lth
O rg a n isa tio n
3 0
A .A . M e h a r g e t a l./E n v ir o n m e n ta l P o llu tio n 9 9 ( 1 9 9 8 ) 2 9 - 3 6
PA H
b a s e
s e t ;
U SD H H S,
1 9 9 5 ,a
b )
a lo n g
a
t r a n s e c t
b is e c tin g
th e
sm oke
p lu m e .
S p a tia l
PA H
d e p o s itio n ,
a n d
th e
r a t i o
o f
v e g e ta tio n /s o il
c o n ta m in a tio n
w ere
m o d e lle d u sin g p h y sic a l-c h e m ic a l d e sc rip to rs.
2 .
M a te r ia ls
a n d
m e th o d s
2 .1 .
A c c id e n t d e s c r ip tio n
T he
f i r e
s t a r t e d
i n
a
w arehouse
o n
th e
9 /1 0 /9 5
a t
05.35 h and w as extinguished by

1 4 .4 0 h . T h e w a r e h o u s e w a s u se d to sto re 10 000 to n o f p o ly p ro p y le n e in p e lle te d fo rm

fo r m o u ld in g . F o llo w in g th e in c id e n t, in fo rm a tio n
o n
p lu m e
d ire c tio n
a n d
w id th ,
a n d
th e
w in d
s p e e d
th r o u g h o u t th e fire w a s o b ta in e d
fro m
the U K
M eteor-
o lo g ic a l O ffic e 's C h e m n e t se rv ic e (B e n n e tt a n d
W eston,
1 9 8 9 ).
S u rfa c e
w in d
s p e e d
fro m
0 8 .4 0 --1 1 .4 0 h
a t
180\u00b0 was
2 8 k m h -1
w ith
g u sts
u p
t o
38km h-1;
a v e r a g e
m ix e d
la y e r
w in d
s p e e d
w as
3 5 k m h -l
fro m
2 0 0 \u00b0 ,
a ir
tem -
p e ra tu re
w as
1 5 \u00b0 C
risin g
t o
1 9 \u00b0C , h u m id ity

85% , pre- c ip ita tio n n il a n d d e p th o f m ix e d la y e r w a s 1 5 0 0 m . T h e su rfa c e

w in d
s p e e d
fro m
1 1 .4 0 - 1 4 .4 0 h
a t
1 9 0 \u00b0
w as
30 km h -1 w ith gusts up to 40 km
h -l, slow ly decreasing
t o
2 0 k m h -1
w ith
g u sts
t o
3 0 k m h -1 .
A verage
m ix e d
la y e r
w in d
s p e e d
w as
4 0 k m h -I
fro m
2 1 0 \u00b0
g ra d u a lly
decreasing to
3 5 k m h -1 . A ir te m p e ra tu re w a s
1 9 \u00b0 C
r i s -
ing to
2 2 \u00b0C , p re c ip ita tio n
n il a n d
d e p th
o f m ix e d
la y e r
w as
15 000 m .
V ertical dispersion
o f th e p lu m e w a s slo w , w h ile h o r-
iz o n ta l d isp e rsio n
w as
m o d e ra te
t o

o c c a s io n a lly ra p id , th r o u g h o u t th e e n tire tim e c o u rse o f th e fire . T h e p lu m e d isp e rsio n

m o d e lle d
b y
C hem net
w as
e n te r e d
in to
a
G e o g ra p h ic a l In fo rm a tio n

S y ste m . P lu m e d ire c tio n w a s p lo tte d in F ig . 1 fo r th e tw o tim e p e rio d s , 0 5 .3 5 -0 8 .4 0 h a n d

1 1 .4 0 - 1 4 .4 0 h .
2 .2 .
S a m p lin g
E n v iro n m e n ta l
sam ples
w ere
c o lle c te d
48 h

a fte r th e in c id e n t. T h e r e w e re n o p re c ip ita tio n e v e n ts b e tw e e n th e s t a r t

o f
th e
f i r e
a n d
sam pling
te rm in a tio n .
S o il
a n d
v e g e ta tio n
sam ples
w ere
c o lle c te d
a t
d is ta n c e s
2 .5 - 4 .6 k m
u n d e r
th e
p lu m e
fro m
th e
w arehouse
a n d
1 -2 .2 k m
i n
th e
o p p o site
d ire c tio n
t o
th e
p lu m e

(1 8 0 \u00b0) (F ig . 1 ). S a m p le s w e re n o t c o lle c te d c lo se r to th e site o f th e

a c c id e n t
a s
th e re
w as
n o
a c c e s s
t o
th e

in d u stria l c o m p le x in w h ic h th e w a r e h o u s e w a s lo c a te d . T h e m o s t d ista n t

sam pling
p o in t
u n d e r
th e
p lu m e
w as
o n
th e

coast line (Fig. 1). The plum e was observed to be carried still fu rth e r o u t o v e r th e se a . S a m p lin g site d e sc rip tio n s are given in Table

1. In p u ts to
the sea surface were not
d e te rm in e d .
S o il
( t o
a
d e p th
o f
10cm )
a n d
g r a s s
s h o o ts
fro m
rough grassland w ere collected at all sam pling points. A

F ig . 1 . P lu m e d isp e rsio n d u rin g th e p o ly p ro p y le n efire . T h e d o t-d a sh lin e s h a d in g in d ic a te s p lu m e d isp e rsio n fro m 0 5 .3 0 -1 1 .4 0 h w h ile th e d a s h e d lin e in d ic a te s d is p e rs io n fro m 1 1 .4 0 -1 4 .4 0h . S a m p lin g s ite s a re n u m b e re d a n d m a rk e d w ith tria n g le s w h ile th e s ite o f th e w a re h o u se is m arked w ith a solid square.

30 m m
d ia m e te r c o re r w a s u se d to o b ta in so il c o re s. T h e
c o r e r
w as
th o ro u g h ly
w ashed
i n
d is tille d
w a te r
a n d
d rie d a fte r e a c h sa m p le w a s ta k e n . T h re e re p lic a te g ra ss
a n d
soil sam ples
w ere
o b ta in e d
a t
e a c h
site , c o lle c te d
along a transect at 10m
s p a c in g . S o il a n d
grass sam ples
w ere collected in glass K ilner jars.
2 .3 .
S a m p le p r e p a r a tio n
Sam ples were
re tu rn e d
t o
th e
la b o ra to ry
o n
th e
d a y
o f sa m p lin g
w here
sub-sam ples
o f b o th
so ils a n d
v e g e -
ta tio n
w ere
im m ed iately
e x tra c te d
w ith
d ic h lo r-
o m e th a n e
(D C M )
i n
p re p a ra tio n
fo r
PA H
a n a ly s is .
A p p ro x im a te ly
40 g
of soil was
w e ig h e d
in to
a
250 m l
glass bottle fitted w ith a T eflon lined screw top. T he soil
was dried
b y
stirrin g
i n
20 g of anhydrous
so d iu m
su l-
p h a te .
H P L C
g r a d e
D C M
(50m l)
su p p lie d
b y
R a th -
b u rn s, U K
w a s a d d e d to th e so il a n d th e c o n te n ts o f th e
b o ttle
w ere
m ix e d
b y
s h a k in g
a n d
in v e rsio n .
T he
A .A . M e h a r g e t a l./E n v ir o n m e n ta l P o llu tio n 9 9 (1 9 9 8 ) 2 9 -3 6
T a b le 1
S ite a n d s o il d e sc rip tio n s fo r sa m p lin g p o in ts s h o w n in F ig . 1
3 1
S am p lin g site
D istance from w arehouse
S ite d e sc rip tio n
S o il ty p e
(k in )
1
1 .0
rough grassland
b o u ld e r c la y
2
1 .9
rough grassland
b o u ld e r c la y
3
1 .6
rough grassland
b o u ld e r c la y
4
2 .4
tille d
silty c la y
5
2 .5
tille d
silty c la y
6
3 .0
w a s te la n d
silty c la y
7
3 .2
w a s te la n d
im p a c te d c la y
8
4 .0
fix e d d u n e
sa n d
9
4 .5
d u n e
sa n d
sam ples
w ere
le ft
o v e rn ig h t
b e fo re
c o n tin u in g
th e
e x tra c tio n
p r o c e d u r e .
T he
so il
w as
th e n
e x tra c te d
a n o th e r
4
tim es
w ith
50m l
a liq u o ts
of DCM .
S a m p le
b la n k s
c o n s is te d
o f e m p ty
K ilner jars
ta k e n
o u t
a n d
o p e n e d
i n
th e
field. Subsequent extraction
a n d

sam ple tre a tm e n t o f b la n k s w a s id e n tic a l to th e e x tra c tio n p ro - c e d u r e s

o u tlin e d
above. There
w as
o n e
b la n k
for soils
a n d
o n e b la n k
fo r v e g e ta tio n .
A p p r o x im a te ly 2 0 g o f v e g e ta tio n w e re w e ig h e d in to a
500m l
K iln e r
ja r
t o
w h ic h
100m l
o f
D C M
(H P L C
g ra d e ) w a s a d d e d a n d th e c o n te n ts o f th e ja r w e re m ix e d
b y
sw irlin g .
T he
sam ples
w ere
le ft
o v e rn ig h t

b e fo re c o n tin u in g th e e x tra c tio n p ro c e d u re . T h e v e g e ta tio n w a s th e n

e x tra c te d
b y th e
sam e
e x tra c tio n
p r o c e d u r e
a fur-
ther 4 tim es.
B o th
th e
so il
a n d
g r a s s
D C M
e x tra c ts
w ere
t r a n s -
f e r r e d
t o
a
500m l
K uderna-danish
f l a s k
v ia
a
fu n n e l
c o n ta in in g
1 0 g
o f
a n h y d r o u s
so d iu m
s u lp h a te .
T he
e x t r a c t
i n
th e
K uderna-danish
f l a s k
w as
r e d u c e d
t o
2 .5 m l
i n
a
w a te r
b a th
a t
5 5 \u00b0 C .
T he
v o lu m e
o f
th e
extract was
r e d u c e d
t o
e x a c tly
2m l
u sin g
a
s t r e a m
o f
e le c tro n
c a p tu re
g r a d e
n itro g e n
(B ritish
O xygen
C om -
pany, U K ).
C le a n -u p
w as
c a rrie d
o u t
b y
a lu m in a
c o lu m n
c h r o -
m atography. The
a lu m in a
was prepared
b y d e c o n ta m i-
n a tio n
in a m uffle furnace at 700\u00b0C
for 4 h
fo llo w e d b y
d e a c tiv a tio n
w ith
th e a d d itio n
of 5%
w a te r (w /w ). T h e
a lu m in a
c o lu m n
c o n s is te d
o f 3 .5 g
o f d e a c tiv a te d
a lu -
m in a p a c k e d
in to
a 7mm
d ia m e te r g la ss c o lu m n .
E x tra c t
(200 #l)
w as
p la c e d
o n
th e
c o lu m n
a n d
th e
P A H s
e lu te d
w ith
5m l
o f
h e x a n e .
T he
e lu a n t
w as
r e d u c e d
to 0.5 ml under a stream
o f n itro g e n . A n
in te r-
n a l
s ta n d a r d
o f 2 ,6 -d ic h lo ro b e n z o n itrile
w as
a d d e d
t o
th e sa m p le s to g iv e a fin a l c o n c e n tr a tio n 0 .5 /z g m 1 -1 .
Recovery and
b la n k
sa m p le s w e re in c lu d e d w ith e a c h
b a tc h
of soil and
v e g e ta tio n
sam ples. M aterial
u s e d
t o
c a lc u la te re c o v e rie s w a s so il a n d
v e g e ta tio n fro m
a rural
site. This m aterial was spiked
w ith
a PAH
m ix tu re a n d
e x tra c te d
id e n tic a lly
t o
th e
sam ples. U nspiked
sam ples
of the
m aterial
u s e d
t o
c a lc u la te
recoveries were
a l s o
a n a ly s e d to
subtract background
le v e ls f r o m
th e s p ik e d
m a te ria l. R e c o v e rie s w e re ru n w ith e v e ry 15 sa m p le s.
Sub-sam ples
o f
so il
a n d
v e g e ta tio n
sam ples
w ere
dried at 70\u00b0C
to a c o n s ta n t w e ig h t a n d
this in fo rm atio n
was used to report PA H
d a ta
on a dry w eight basis.
2 .4 .
P A H
a n a ly s is
T he
G C -M S
m odel
w as
a
H ew lett
P a c k a r d
(U K )
5 8 9 0
g a s
chrom atograph
in te rfa c e d
t o
a
5 9 7 2
m ass
s e le c tiv e
d e te c to r.
A n
a u to s a m p le r
w as
u s e d
t o
in je c t
5 #1
of sam ple. The
in je c tio n
te c h n iq u e
w as
s p lit/s p lit-
less at 250\u00b0C. The colum n was a 30m \u00d70.25m m
id H P 5
M S
fitted w ith
a 5 m \u00d7 0 .2 5 m m
id d e a c tiv a te d re te n tio n
g a p .
T he
carrier gas
w as
h e liu m
h e ld
a t
1 .7 5 m lm in -I
th ro u g h o u t th e ru n
by electronic pressure
c o n tro l. T h e
c o lu m n
o v e n
w as
h e ld
a t
4 0 \u00b0 C
fo r
2 m in
a n d
th e n
ram ped
at 10\u00b0Cm in -1 to 300\u00b0C. The m ass spectrom eter
was run
i n
select ion
m ode. The
3 m ost abundant
io n s
w ere
m o n ito re d
fo r
e a c h
com pound
except for
n a p h -
th a le n e
w here
o n ly
2 ions were
m o n ito re d . T h e
P A H s
d e te rm in e d
are reported in Table 2.
T he
id e n tity
of a
c h ro m a to g ra p h ic
p e a k
w as
id e n ti-
fied by com parison
o f th e p e a k 's re la tiv e re te n tio n tim e
w ith
th e
re la tiv e
re te n tio n
tim es
of peaks
i n
th e
s ta n -
d a r d .
T h is
o p e ra tio n
w as
perform ed
a u to m a tic a lly
b y
th e
G C -M S
chrom atography
d a ta
s y s t e m
a n d

chrom a- to g ra m s w e re c h e c k e d m a n u a lly b y o v e rla y in g th e sta n - d a r d

a n d
sa m p le c h ro m a to g ra m s . R e te n tio n
tim e of the
in te rn a l
s ta n d a r d
w as
u s e d
t o
c o rre c t fo r v a ria tio n
i n
re te n tio n tim e . C o m p a ris o n
o f the ion ratio s o f the rele-
vant standard
p e a k
w ith the ion
ra tio s o f th e u n k n o w n
i n
th e
sam ple
were used
a s c o n firm a tio n
of peak
id e n -
tity. T he
p e a k
a r e a
of the
m ost abundant
of the

th re e io n s m o n ito re d (ta rg e t io n ) w a s u se d fo r a ll q u a n tita tiv e c a lc u la tio n s .

3 .
R esu lts
a n d
d iscu ssio n
Levels of 16 PA H s
in so ils a n d
v e g e ta tio n a t th e d if-
fe re n t sa m p lin g
p o in ts
w ere
d e te rm in e d
a n d
re la te d
t o
th e
p lu m e
d istrib u tio n
p lo t
(F ig .
1). The
g r a p h s
illu s-
tra tin g
th e
PA H
d istrib u tio n
(F ig .
2 )
a re
r a n k e d
i n

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