Welcome to Scribd, the world's digital library. Read, publish, and share books and documents. See more
Download
Standard view
Full view
of .
Save to My Library
Look up keyword
Like this
3Activity
0 of .
Results for:
No results containing your search query
P. 1
Image Decomposition of PAHs in Soil and Desorption of Organic Solvents Using Microwave Energy

Image Decomposition of PAHs in Soil and Desorption of Organic Solvents Using Microwave Energy

Ratings: (0)|Views: 57 |Likes:
Published by api-3721576

More info:

Published by: api-3721576 on Oct 18, 2008
Copyright:Attribution Non-commercial

Availability:

Read on Scribd mobile: iPhone, iPad and Android.
download as PDF, TXT or read online from Scribd
See more
See less

03/18/2014

pdf

text

original

C hem m phere, V ol. 39, N o. I, pp. 81-87, 1999
Q 1 9 9 9 E ls e v ia
S c ie n c e L td . A ll rig h ts re s e rv e d
0 0 4 5 -6 5 3 5 /5 9 / s - s e e fru n t m a tte r
P II: !a o 4 5 -6 5 3 5 (!9 8 )0 0 5 9 0 -6
IN SITU
D E C O M P O S IT IO N
O F P A H s IN
S O IL A N D D E S O R P T IO N
O F
O R G A N IC S O L V E N T S U S IN G M IC R O W A V E E N E R G Y
R U D O L P H A . A B R A M O V l T C H , * H U A N G B A N G Z H O U ,D O R O T A A . A B R A M O V I T C H \u2019 a n d
S O N G JIA N G A O
*D epartm ent
of C hem istry,C lem son U niversity,C lem son,S C
2 % 3 4 -1 9 0
\u2018D epartm entof Science and M athem atics,A nderson C ollege, A nderson, S C 29621
(R eceived in G em any
24 August 1998; accepted 15 O ctober 1998)
A b s tra c t.
T he
d e c o m p o s itio n
o f
in d iv id u a l
P A H \u2019s
(ber@ aJpyrene,
b e n x o ~ flu o ra n th e n e ,
d ib e n z ~ h J a n th ra c e n e .
benz@ m hracene,
I-n itro p y re n e
a n d
b e n x o ~ q u in o lin e )
in soil
i n
a n
o p e n
v e s s e l
u s in g
m ic ro w a v e
e n e rg y
is re p o rte d .
N o
P A H \u2019s
rem ain
in the
s o il a fte r re m e d ia tio n .
A n
a tte m p t
t o
u se
\u201c C -1 a b e lle d
b e n z o ~ p y re n e
t o
d e te rm in e
th e
f a te
o f
th a t
c o n ta m in a n t
o n
m m e d ia tio n
le d
o n ly
t o
th e
o b s e rv a tio n
o f
th e
fo rm atio n
o f 0 .3 %
of \u201c C O z.
N one
o f th e o th e r
d e c o m p o s itio n
p ro d u c ts
c o u ld
b e e x tra c te d ,
is o la te d
o r q u a n titie d .
U sin g
a s im ila r p ro c e d u re ,
a variety
o f o rg a n ic
s o lv e n ts
(c y c lo h e x a n e ,
l,l,l-tric h lo ro e th a n e ,
te tra c h lo ro e th y le n e ,
b e n z e n e ,
to lu e n e
a n d
x y le n e )
c o u ld
b e
e ffic ie n tly
d e s o rb e d
a n d
c o lle c te d
fro m
c o n ta m in a te d
s o i l .
T h e s e
e x p e rim e n ts
o ffe r a v a lid m o d e l fo r th e in s itu re m e d ia tio n
of these
p o llu ta n ts
fro m
c o n ta m in a te d
s o i l .
_ -
0
1 9 9 9 E ls e v ie r
S c ie n c e
L td . A ll tig h ts
re s e rv e d
In tr o d u c tio n
A
large number
o f s tu d ie s
h a v e
b e e n
c a rrie d
o u t
o n
s o il
m m e d ia tio n
a n d
th o s e
fo r
P C B s
h a v e
b e e n
sum m arixed
in a n e a rlie r p a p e r.\u2019
B io re m e d ia tio n
o f p o ly c h lo rin a te d
b ip h e n y ls
(P C B s)
a n d
p o ly c y c lic
arom atic
h y d ro c a rb o n s
(P A H s)
in s o il h a s b e e n
d is c u s s e d .2
A n
assessm ent
o f th e
v a rio u s
in d u s tria lly -d e v e lo p e d
b e n c h -
s c a le te c h n o lo g ie s
fo r m m e d ia tio n
o f s e d im e n ts
c o n ta m in a te d
w ith
P C B s
and PA H s
has been
c a rrie d
o u t.\u2019
T h e s e
in c h & d
th e
B .E .S .T .\u2019
s o lv e n t
e x tra c tio n
p ro c e s s
u s in g
trie th y la m in e , th e
R eT ec
lo w
te m p e ra tu re
therm al
d e s o rp tio n
te c h n o lo g y ,
th e
H o lo -F lite m
s c re w
p ro c e s s o r
m e th o d ,
th e
Z IM P R O
w et
o x id a tio n
p ro c e s s
w h ic h
o x id iz e s
in o rg a n ic
a n d o rg a n ic
c o n ta m in a n ts
under aqueous
c o n d itio n s
at 175-320\u2019 C and pressures
of 20 M Pa,
a n d
S o ilT e c h \u2019s
a n a e ro b ic
therm al
p ro c e s s
(A T P )
te c h n o lo g y .
T he
r e s u lts
w ere
v a ria b le .
F o r
e x a m p le ,
R eT ec\u2019s
p ro c e s s o r
d e s o rb e d
> 9 6 %
o f th e P C B s
a n d
% O%
o f th e
P A H s,
w h ite
Z IM P R O \u2019s
o x id a tio n
p ro c e s s
decom posed
o n ly
2 9 %
o f th e P C B s b u t > 9 8 .9 %
o f th e
P A H s.
E trN
s o lv e n t
e x tra c tio n
rem oved
9 5 4 9 %
o f th e
P C B s
and 65-
9 0 %
of the PA H \u2019s.
W e h a v e re c e n tly
re p o rte d
a m odel bench-scale
m e th o d
fo r
th e
i n
s i t u
re m e d ia tio n
o f
s o ils
c o n ta m in a te d
_ -
w ith P C B s a n d o th e r c h lo rin a te d
a ro m a tic s
using m icrow ave
e n e rg y .\u2019
W e now
report the extension
of these
s tu d ie s
to th e re m e d ia tio n
o f s o ils c o n ta m in a te d
w ith P A H s , a s w e ll a s to th e d e s o rp tio n
o f o rg a n ic
s o lv e n ts
tio m
s o ils .
8 1
8 2
E x p e r im e n ta l S e c tio n
M icrowrveD ecom podtionofP AH r
B enzo@ Jpyrene,
b e n z o ~ flu o ra n th e n e ,
diben& hJanthracene,
benz@ m hracene,
1n itro p y re n e
a n d
benxo[flquinobne were purchased from AccuStandard Inc., New Haven, CT.
T h e s o il w a s c o lle c te d fro m a ro u n d
th eClem son University cam pus and cleaned as described previously.\u2019
T h e c le a n e d s o il
w as shown to be free of
any extractable PA H s.
F o r th e re m e d ia tio n o f s o il c o n ta m in a te d w ith P A H s th e p ro c e d u re u s e d w a s th e s a m e a s th a t d e s c rib e d fo r
the bench-scale h
&
re m e d ia tio n o f P C B s -c o n ta m in a te d so il.\u201d
T h e c le a n s o il w a s s p ik e d w ith th e in d iv id u a l th e
b e n c h -s c a le in s itu re m e d ia tio n o f P C B s -c o n ta m in a te d s o il.\u2019
- -

T h e c le a n s o il w a s s p ik e d w ith th e in d iv id u a l P A H (th e P A H w a s d is s o lv e d in re d is tille d , d rie d C H 2 C ls .th e s o h ttio n w a s a d d e d to th e s o il w h ic h w a s th e n th o ro u g h ly m ixed and air dried, eventually under w ater pum p vacuum at room tem perature to constant w eight). For exam ple, s o il (8 g ) w a s s p ik e d w ith b e n x o [a lp y tc n e (1 .0 0 8 m g ). S e e T a b le1 fo r o th e r lo a d in g ra te s .

In ah cases, the spiked
s o il w a s le ft to s ta n d fo r m o re th a n a w e e k b e fo re e x tra c tio n o r m ic ro w a v e irra d ia tio n to \u2018a g e \u2019 it.
A n a h q u o t o f th e
spiked soil w as extracted repeatedly
w ith p u re C H & ,
th e s o lu tio n c o n c e n tra te d a n d a n a ly z e d q u a n tita tiv e ly
b y
g a s c h ro m a to g ra p h y to re c o v e r th e P A H a lm o s t q u a n tita tiv e ly
(biphenyl w as used as the internal standard for the
q u a n tita tiv e a n a ly s is ). T h e s p ik e d s o il (8 .0 g ) w a s p la c e d in th e q u a rtx in s e rt o f th e v e s s e l in F ig
2 of ref. 4 and
th e n tre a te d w ith a s o lu tio n o f N a # O 4 (2 0 0

m g ) in w a te r (2 .2 m l). O n e p e n c il le a d (fro m a # 2 p e n c il) (3 .9 c m lo n g , 2 .0 m m d ia .)\u2019 w a s in s e rte d in th e s o il s u c h th a t it w a s c o v e r e d b y a th in la y e r o f s o il. T h e v e s s e l w a s th e n p la c e d in a K enm ore dom estic m icrow ave oven (m ax. pow er 750 w ), covered w ith the funnel and condenser (Fig 2 of ref. 4), th e c o n d e n s e r e n d w a s c o n n e c te d to a w a te r p u m p , a n d th e m ix tu re w a s irra d ia te d a c c o rd in g to th e tim e a n d p o w e r s e q u e n c e

in d ic a te d
in
T a b le
I .
A fter
th e
m ix tu re
h a d
c o o le d
t o
ro o m
te m p e ra tu re ,
th e
c o n d e n s e r
a n d
fu n n e l/d is tilla tio n
arm w ere w ashed separately
w ith p u re C H 2 C 1 2 ,
a n d th e m o s tly
v itrifie d s o il w a s c ru s h e d a n d
e x tra c te d re p e a te d ly
w ith
th e s a m e s o lv e n t.
The washings/extracts were concentrated
a n d
each was analyzed
q u a lita tiv e ly ( G C I M S ) a n d q u a n tita tiv e ly \u2019
(G C ).

The sam e procedure w as used for all the PA H s tested, and the results are sum m arized in T able 1 (only a few representative runs are show n: m any m ore w ere actually carried out w ith s im ila r re s u lts ). R u n s w e re a ls o c a rrie d o u t u sin g iro n w ire (o n e ru n w ith c o p p e r w ire ) in s te a d o f p e n c il le a d , a s w e re b la n k ru n s (n o P A H s ) to d e te rm in e w h a t p ro d u c ts m ig h t d is til o r b e e x tra c te d fo llo w in g re m e d ia tio n .

Iro n
w in s
(6.5 x 2.0 m m ) w ere inserted in the soil so that the tops w ere just below the surface.

A fte r m u c h o f th e w ater had evaporated, the soil w as irradiated in the K enm ore dom estic m icrow ave oven (750 w m ax.pow er) for 10 m in a t 5 % p o w e r , 1 0 m in a t 1 0 % p o w e r , 1 0 m in a t 3 0 % p o w e r a n d I O m in a t 1 0 0 % p o w e r .

A fter the m ass had
c o o le d to ro o m te m p e ra tu re th e s o il w a s fo u n d to h a v e v itrifie d to a h e ig h t o f 5 .5 -6 .0 c m , w h ile th e to p
l - l .5
a n
w a s n o t v itrifie d .
M k ro w rv e
D e c o m p o d tia a
of B eazo~pyrene-7-\u201c C .
8 3
T h e l~ b e lk dc o m p o u n din s o lu tio n w a s p u r c h a s e dfr o m S ig m a .T h e s o lu tio n w a s d ilu te d toI m l w ith p u re ,
d ry
to lu e n e
re a u h in g in a n a c tiv ity
o f 5 0 m C i/m l.
1 0 0 m l o f th e s o lu tio n
w a s a d d e d to
a s o lu tio n
of non-
radioactive benzoupyrene
( 0 .6 4 m g ) in C H $ &
(7 m l), a n d th is w a s a d d e d to 5 g o f c le a n s o il.
O ne g of spiked
so il (2 m C i) w a s e x tra c te d w ith
p u re C H sC lz , tre a te d w ith
s c in tilla tio n
fluid (E colite; IC N
cat. # 882475) and
c o u n te d in a B e c k m a n L iq u id S c in tilla tio n c o u n te r L S - 3 1 3 3 L .
Seventy-five percent of the benzoupyrene
w as
e x tra c ta b le ;
the rest w as probably
h e ld tig h tly
b y
the soiL6
T hree gm m s of spiked
soil w ere treated w ith a
s o lu tio n
of N a$O a
(7 5 m g ) in w a te r (0 .6 m l), p la c e d in th e q u a rtz
vessel and pencil lead w as inserted (U .S.A .
S u p e r L o & b o n d W a lla c e lN V A D E R 5 \u201d # 3 ).
(N O TE: This is m uch narrow er than the #2 pencil lead used above,
re s u h in g in th e s o il n o t b e in g h e a te d to th e s a m e h ig h te m p e ra tu re s
a s in th e n o n -la b e lle d m a te ria l e x p e rim e n ts .
T h is w a s d o n e s o a s to e n s u re th a t n o t a ll th e b e n z o [_ a ]p y re n ew a s d e c o m p o s e d in th e s o il, to try
a n d d e te rm in e if
fra g m e n ts o r tra n sfo rm a tio n p ro d u c ts c o u ld b e o b s e rv e d ).
A fter allow ing the soil to stand for lh, it w as irradiated
w ith m icrow ave energy as before: 5 m in (20% pow er), 5 m in (30% ). and 3 m in (100% ).
T h e s o il w a s a llo w e d to
c o o l a n d th e n th e c o n d e n s e r a n d fim n e lk iis tilla tio n
arm w ere w ashed repeatedly w ith pure C H & 12,and the soil w as
e x tra c te d s e p a ra te ly c o n tin u o u s ly w ith th e s a m e s o lv e n t.
C o u n tin g o f th e e x tra c ts s h o w e d th e p re s e n c e o f 1 .4 % o f
th e o rig in a l ra d io a c tiv ity in th e d is tilla te s, a n d 4 3 .4 % in th e s o il e x tra c ts .

W hen the procedure w as repeated and the off-gases passed also through a0 .1 N N aO H solution in a tube connected to the condenser, so that gases evolved were swept through by

th e lo w
v a c u u m
p a s s e d
th ro u g h th e a lk a lin e s o lu tio n
aR er any
b e n z o ~ p y re n e
a n d /o r
decom position products had been trapped
in the condenser, 0.3%
o f th e to ta l ra d io a c tiv ity w a s tra p p e d
as C O z.
G C lM S
a n a ly s is o f th e c o n d e n s e d d is tilla te s a n d o f th e s o il e x tra c tiv e s in d ic a te d th a t
th e y
w ere virtually
a ll
unchanged benxo~pyrene.
A c id ific a tio n o f b a s itic a tio n o f th e re m e d ia te d s o il fo llo w e d b y
e x te n s iv e e x tra c tio n
fa ile d to y ie ld a n y a d d itio n a l e x tra c ta b le m a te ria l, n o t w a s a n y m o re 1 4 C 0 2 re le a s e d .
As before:

attem pts w ere m a d e to d e te c t a n y o th e r m a te ria l re m a in in g in th e s o il b y d is s o lv in g th e re m e d ia te d s o il in a q u a re g ia , d ilu tin g th e suspension som ew hat (the soil precipitated

o u t o n g r e a te r d ilu tio n ), a d d in g s c in tilla tio n flu id a n d c o u n tin g b u t, a s b e fo re , n o ra d io a c tiv ity w a s d e te c te d , p ro b a b ly o w in g to th e s c in tilla tio n flu id u s e d n o t b e in g s ta b le to th e s tro n g ly a c id ic c o n d itio n s .

T h u s , a p p ro x im a te ly 5 5 %
of the benz~pyrene
d e c o m p o s e d b u t o n ly
a trace am ount of that
could be accounted for, in the form of C02.
D e a o rp tio oo f O r g a n ic S o lv e n ts fto m S o il U s in g M k r o w a v e E n e r g y
In d iv id u a l s o lv e n ts (I g ) w e re p la c e d in th e q u a rtz tu b e (F ig . 2 o f re f. 4 ) a n d c o v e re d w ith c le a n s o il (1 0 8 )\u201c\u2019
w h ic h re a c h e d to a h e ig h t o f 5 .5 c m a b o v e th e b o tto m
o f th e tu b e . T h e a p p a ra tu s w a a m o d itie d b y
a d d in g th re e
m omcondcnaer
veesels in series to the one in Fig. 2 of ref. 4, and anaching the w ater pum p
to the last of the four
c o n d e n s e rs .
T h e
tin t
condenser was
c o o le d in
ice-water, the
s e c o n d
in
a n d
ic e -s a lt
b a th ,
a n d
th e
th ird

You're Reading a Free Preview

Download
/*********** DO NOT ALTER ANYTHING BELOW THIS LINE ! ************/ var s_code=s.t();if(s_code)document.write(s_code)//-->