Chlorinated compounds in emissions from municipal incineration

Chemosphere,Vol.12,No.4/5,~p Printed in Creat Britain

665-668,1983

OO45-6535/83/O50665 O4503.OO/O ©1983 Pergamon Press Ltd.

CHLORINATED COMPOUNDS IN EMISSIONS FROM MUNICIPAL INCINERATION

Ulla Samuelsson and Anne Lindskog Swedish Water and Air Pollution Research I~stitute P.O. Box 5207,S-40224 Gothenburg, Sweden

INTRODUCTION Three emission samples from a municipal incinerator have been analysed for neutral components. The plant was equipped with an inclined grate furnace followed bY3an afterburner. The furnace load was 2000 kg/h and the stack gas flow 30 000-35 000 m /h (stp). EXPERIMENTAL Sampl i ng p a r a m e t e r s :

Sample

I 2 3

Temp. in the flue gas °C = 200 ~200 =200

Temp.in the furnace °C

CO 2 %

820-900 700-800 680-780

5-6 6-7 5-6

SampleVolume m3(stp)d.g • I0 12 9

Sampling e q u i p m e n t : Glass f i b e r

filter

Condensate Amberlite

~::

(I) (2)

XAD-2

(I)

(3)

IIL,] 665

666

The f i l t e r s and the XAD-2 columns were Soxhlet e x t r a c t e d f o r 24 h w i t h dichloromethane and the condensate was e x t r a c t e d by shaking w i t h cyclohexane. The e x t r a c t was t r e a t e d w i t h 0.5 M NaOH-solution to remove the acids and w i t h I M H~SOA-solution to remove the bases. The remaining n e u t r a l f r a c t i o n was concentrated and th~ dTchloromethane was replaced by cyclohexane. A p o r t i o n of the concentrated f r a c t i o n was in some cases f u r t h e r f r a c t i o n a t e d on a s i l i c a column (5% w a t e r ) e l u t e d w i t h n-hexane, toluene and dichloromethane. The d i f f e rent f r a c t i o n s were analysed by GC and GC/MS. The GC:s used were Carlo Erba Fractovap w i t h a FID and a glass c a p i l l a r y column (SE-54) and Varian 3700 w i t h an ECD and a glass c a p i l l a r y column (SP 1000). The GC/MS was a Hewlett Packard 5992A w i t h a f l o p p y disc system, s p l i t l e s s i n j e c t i o n and a fused s i l i c a c a p i l l a r y column (SE-54), operated in both peakf i n d e r mode and s e l e c t e d ion m o n i t o r i n g mode. The exact c o n c e n t r a t i o n of i n d i v i d u a l components was concidered less i m p o r t a n t and the demand of a precise q u a n t i f y i n g was r e j e c t e d in f a v o r of the p o s s i b i l i t y to f a c i l i t a t e the i d e n t i f i c a t i o n by clean-up procedures. RESULTS AND CONCLUSIONS The amount and number of organic compounds were d i f f e r e n t in the three samples but the g r e a t e s t p a r t of the organic content was always found in the XAD-2 e x t r a c t f o l l o w e d by the condensate e x t r a c t . Only a minor p a r t was found in the p a r t i c l e e x t r a c t . To e s t i m a t e the t o t a l emission i t is thus necessary to analyse both the p a r t i c u l a t e phase and the vapor phase. Emission data:

Sample

pg/m3 (stp) d, 9. 10% CO2 I

2 3

Phenantrene

Hexach|orobenzenes p~/MJ

~/m 3 (stp) d.g. 10% CO2

pgl;,IJ

6

4

5

4

60 110

45 80

40 100

30 75

Q u a n t i t a t i v e l y the n e u t r a l f r a c t i o n dominates by a l i p h a t i c hydrocarbons and PAH. C h l o r i n a t e d compounds were found in a l l the samples wich i n d i c a t e s a general f o r m a t i o n . The amount was less than 10% and the d i f f e r e n t groups can q u a n t i t a t i v e l y be arranged in the f o l l o w i n g o r d e r : c h l o r l n a t e d benzenes > PCDF > PCN > PCDD > PCB.

Reconstruction of p e a k f i n d e r

ION 3 3 9 . 9

PCDF

FS

in sample 3

~ sO: ii : i! .' ;{ ! V'-!::

100

ION 3O5.9 FS

! 4

C1

50

ION 269.9

i 3 C1 - ~

JJ

ION 236.0

q

~:12 Cl

mi'.~ ,.

.,

M

='.~ :

,,. .

.

!.,i:.. ~'' ~ '*".._:

667

~oN 35<9

Reconstruction of peakfinder

Fs

PCDD in sample 3

: 5 cl

il i '%ii

I0

f I .;

i i[

ION 321.9

" ~.

,o

~i4 Cl

ION 285.9 FS

10 ............ ~: :'~

ION 252.0 FS 5 #,..,

Reconstruction of peakfinder

ION 459.7

PCDF + PCDD in sample 3

FS

it ~.

T','"

~ "~"

iV= "~ii' ! i v ' ' 8 Cl

!t

20

/. ~_..

ION ,423.8 OCDD seems to have a more s t a b l e c o n f i g u r a t i o n than OCDF

FS

,7CI R

20

ION 389.8 tl

FS

20

•

6 C1

~\ :,~,

ION 443.7 FS

8 C1

A

20

,'. ~-

ION 4})7.8 FS 75

17 Cl ;t,

ION 373.8

i 6ACI

FS

;\ : k;,

75

Selected ion monitoring, ion 305.9 TCDF and 2.3.7.8-TCDF

f~ tl

;',

',i,

,,,.

~r,

',i ~.~ ,in ,~

i':q il. i[!~,i!i i!!i r

~.,t

L, i i ~ f

b

,-i

The maximum amount of 2.3.7.8-TCDF in sample 3 is about 2 #g/m3 (stp)

66R

The GC-MS analyses a l s o i n d i c a t e the presence o f o t h e r c h l o r i n a t e d compounds. Some o f them have t e n t i t a t i v e l y been i d e n t i f i e d as c h l o r i n a t e d isomers of f l u o r e n o n e , benzonitrile and a l l y l b e n z e n e ( o r f u r a n e ? ) , a l l in a p p r o x i m a t e l y the same amount as PCDF, and p e n a n t r e n e / a n t h r a c e n e , much less than PCDF. Reconstruction of peakfinder, c h l o r i n a t e d f l u o r e n o n e in sample 3.

~5i Cl

ION 351.9

Z

£S

25

:' A

ION 317.9 FS

~ 4 Cl h

30

}]\!~'<< i:, TON 281.9 FS

,{ 3 C i ::

75

tl

zoN 248.o i2 ci~ FS

75

~:: :Ill i

~,~J,.i~% .:v . '.-..,.,~,._..,-,-,,...,..,,,~_,~.~ ~ _,~.~.,::.__. ~ , ' ~ : : .....:........ I Cl-fluorenone base peak 214

..............................................

~ ..................................................

50 i O~J 15~-J 2@LI 2 '-;(~ iigl#_I .::50 ...........................................................................................

4L18

4 Cl-benzonitrile base peak 241

ii 50

1 @O

ii 15E~

IL~ 200

25(I

-',~(~

:350

400

I

6 Cl-allylbenzene (or 6 Cl-furane?) base peak 324

iL

' It

iL

,,I,

,

5C~ i 0C I 150 200 25@ :300 1:5 ;11 .............................................................................................

40~

I Cl-phenantrene/ anthracene base peak 212

5~

i O@

150

2@i~

250

!:~IL1

ACKNO~,EEDGEMENTS This study was supported by a g r a n t from the Swedish N a t i o n a l Environment P r o t e c t i o n Board.

:350

4El ;1