Characterization of halogenated organic acids in flue gases from municipal waste incinerators

Chemosphere,Vol.16,No.6,pp P r i n t e d in Great Britain

i181-i192,1987

CHARACTERIZATION FLUE

Jacques

GASES

OF

FROM

0 0 4 5 - 6 5 3 5 / 8 7 $3.00 + .OO P e r g a m o n J o u r n a l s Ltd.

HALOGENATED

MUNICIPAL

ORGANIC

WASTE

ACIDS

IN

INCINERATORS

M o w r e r I* and Jan N o r d i n 2

Iswedish P.O.Box

E n v i r o n m e n t a l R e s e a r c h Institute, 5207, S-402 24 G6teborg, Sweden

2Swedish P.O.Box

Pulp and Paper R e s e a r c h I n s t i t u t e 5604, S-114 86 Stockholm, Sweden

Abstract A m e t h o d is developed, using c h l o r o a c e t i c acids as model compounds, for the a n a l y s i s of h a l o g e n a t e d o r g a n i c acids in flue gases from waste incineration. Levels of c h l o r o a c e t i c acids in four samples ~aken from the m u n i c i p a l i n c i n e r a t o r at Bor&s range from 4.9 to 17 wg/m-. E i g h t e e n other h a l o g e n a t e d c o m p o u n d s are also i d e n t i f i e d via gas c h r o m a t o g r a p h y - m a s s s p e c t r o m e t r y (GC-MS), as well as n o n - h a l o g e n a t e d precursors. C h l o r o b e n z o i c and c h l o r o b e n z e n e d i c a r b o x y l i c acids are the p r e d o m i n a n t forms. It is b e l i e v e d that many of the h a l o g e n a t e d o r g a n i c acids i d e n t i f i e d can arise from the h a l o g e n a t i o n of b r e a k d o w n p r o d u c t s of p h t h a l a t e s in the i n c i n e r a t o r oven. To the best of our knowledge, the m a j o r i t y of the h a l o g e n a t e d acids i d e n t i f i e d in this study have not been p r e v i o u s l y d e t e c t e d in e n v i r o n m e n t a l samples. N o t h i n g is k n o w n of their d i s t r i b u t i o n in the e n v i r o n m e n t or about the e n v i r o n m e n t a l c o n s e q u e n c e s thereof. Key words Waste

incineration,

flue gases,

halogenated

organic

acids,

air pollution.

Introduction

Municipal

incinerators,

disposal,

have

discovery

of the h i g h l y

thought

themselves

become

toxic

pollutants. (PCN),

interest

chlorinated

polyaromatic quantified

benzenes,

hydrocarbons

in the smoke

in the p r e s e n c e

Polychlorinated

solution

a part of the p o l l u t i o n

to w a s t e problem.

2,3,7,8-tetrachlorodibenzo-p-dioxin

2,3,7,8-tetrachlorodibenzofuran led to i n c r e a s e d

to be an ideal

biphenyls

those

(3,4).

i181

of other

(PCB),

chlorinated

are a m o n g

stack

emissions

phenols that

and

(1,2)

halogenated

polychlorinated

The

has

organic

naphthalenes

and c h l o r i n a t e d

have

been

identified

and

1182

Few s t u d i e s acids

have e x a m i n e d

have been m e a s u r e d

part of the total o r g a n i c acids presence

of these

and to w h a t

organic

a l s o occur,

o r g a n i c acids at some

emission

(4).

where

no one has

The p u r p o s e of this

chlorinated

F o r m i c and a c e t i c

they

form a large

It is p o s s i b l e that c h l o r i n a t e d

but to our k n o w l e d g e

compounds.

extent

in flue gases.

incinerators,

o r g a n i c acids

reported

the

study is to d e t e r m i n e

are p r e s e n t

in smoke

if

stack

emissions.

Mono-,

di-,

and t r i c h l o r o a c e t i c

in the d e v e l o p m e n t compounds

was

Confirmation other

carried

have b e e n c h o s e n as model method.

Quantification

out by GC w i t h e l e c t r o n - c a p t u r e

of the p r e s e n c e of these c o m p o u n d s

chlorinated

concentrations of o t h e r

acids

of the a n a l y t i c a l

organic

acids was

of the c h l o r i n a t e d

chlorinated

compounds

performed

and

detector.

identification

by GC-MS.

a c e t i c acids

was

compounds

of these

of

The

then c o m p a r e d

to those

in the stack gases.

Samplinq

Samples, Sweden,

previously w e r e used

t a k e n at the

in this

study.

city of Bor&s m u n i c i p a l A total of

but only

four of these w e r e a v a i l a b l e

sampling

parameters

summarized Lund~n,

Table

~imple

I.

in Table

1985

and i n c i n e r a t o r

Sampling

Date

9

oven o p e r a t i n g

I. A c o m p l e t e d e s c r i p t i o n

parameters

Time

and

parameters

The

are

is given by B o s t r o m and

12.30-15.30

May 13,-85 08.30-11.45

incinerator

operatinq

conditions.

Air volume I

Volume

Incinerator

Incinerator

Waste 4

Excess

sar~oled

condensate

oven

oven

throuqhput

oxygen

collected

te~rature

operating

(ml)

(°C)

(m3)

May 7,-85

had been taken,

for o r g a n i c acid analysis.

(5).

~.

3

12 s a m p l e s

incinerator,

t/h

%

Smoke stack I

emission m3/h

conditions

2.08

378

900-1100

normal 2

0.92

285

540-980

star~-up 3

22.8

15

32100

8.5

18

6290

]0

- " -

12.00-15.10

1.27

249

990-1100

normal 3

6.5

17

15890

11

- "

15.30-18.30

1.39

279

980-1100

normal 3

8.0

17

14310

I

volun~s normalized to 10% 002 in dry gas, 0°C, 100 kP pressure

2

all three ovens operating

3

only oven No. 3 in operation

4

household garbage

1183

The

samples

were

three-oven

I0-20°C the

Research

a glass using

w]latile

Germany).

directly

incJnerator,

Environmental passes

taken

fiber

with

there.

The

The major condensate,

filter

compounds

absolute ethanol

part

that The

are

sampling,

to collect

is then

was

stored

added

acids

was

in a brown

developed

then

is c o l l e c t e d

on A m b e r l i t e walls

downstream

I). The gas

particulates,

condensate

trapped

of the organic

which

traps

canal

equipment

(see figure

the glass

ethanol

rinse

the flue--gas

sampling

Institute

a condenser.

After

rinsed

using

in

XAD-2

of the

to the

at the

stream

Swedish

first

is cooled

in a flask, (Fluka,

sampling

substances

of the

West

device

that may

to and

are

have

fastened

condensate.

expected bottle

to be found

in the

at ca 4°C prior

to

analysis.

Fiqure

I. D e s c r i p t i o n of a p p a r a t u s used for taking samples in the canal of the m u n i c i p a l i n c i n e r a t o r at Bor~s, Sweden.

direction

!

of ~as

u

flue mas

flow

....

glass and teflon tubino

alass fiber filter

k< XAD-2

filter

pump

condensate ~

meteraaS volu~

1184

Analysis

All

chemicals

diethyl

and

ether

diazomethane

of

by

GC-analysis

Diazomethane

dropwise

g potassium

The

resulting

and

screw

within

one

both

explosive

highly

caps

capture

was

detector, were

temperature

Identification

bonded phase ion

fused

of

to

the

1500

on

60°C

at

a flow

acids

GC-MS

line

temperature

290°C,

15°C/minute

to

electron-impact

the

second.

gas,

instrument

Extraction

with

by

adjusted 2 x

10 m i n u t e s weakly then

the

adjusted

inside

from

Lindstr6m 7-8

and

using

diethyl

100

compounds, to 0 . 8

by

650

the

osterberg

the

ether

phases,

addition

The of

is

acids.

The

i.d. ) p a c k e d

and

The

the

The

GC

carrier

a Finnigan

a 25 mm

(6).

held

the

program

45

to to

I

280°C. 650

methane at

0.8

based

pH

of

condensate

In

amu as

a

torr,

the

on

the

was screw

containing of

um

and

second.

was

The

0.25

into

up

using

every

TSQ

temperature

from

was

acids

pH

i.d.,

temperature

mode,

46

m chemically

directly

wit]] P F T E - l i n e d

discarded.

dropwise

the

tubes

electron-

mesh.

5°C/minute

once

(1986)

63

2500C,

0.32

scanned

organic

of

bath.

safety

80/100

injector

source

amu

15 m]. of

in a t u b e

were

ion

ether

which

acetic

using with

oven

was

,_~

Diazomethane

a Ni

(2 m m

drawn

then

ionization

the to

of

NaOH.

ether

centrifugation,

acidic

chemical

USA)

GC

test

4°C/minute.

silicone,

50°C,

instrument

derivatization

to

3 ml

In

the

pressure

scanned

and

developed was

the

mode

with

W,

of

30 m l / m i n u t e .

follows:

then

20°C,

taken.

performed

Inc., as

ml

Necessary

were

at

of

in use.

compound,

column

with

a solution

this

equipped

methyl

were

to

chlorinated

170°C

use,

in a w a t ~ r

collected

equipped

rate

was

W Scientific

parameters

50°C

temperature

to

(-MS),

(DB-I,

to

Chromosorb

detector

transfer

every

Thirt-y

with

discarded.

glass

to

treatm~_nt

in d i e t h y l

prior

of

the

from

organic

J and

was

-18°C was

long

at

reagent

by from

stirrer

carcinogen,

quantify

200°C,

column

at

handling

a 2 m

in argon,

GC

and

Carbowax was

silica

The

stored

250°C,

once

freedom

heated

preparation

via

Quadrupole)

thickness,

source.

ethanol,

minute the

Prior

tested

by d e s t i l l a t i o n .

chromatograph,

programmed

5% m e t h a n e

Stage

used

0.1%

temperature

(Triple

~nsure

a magnetJ+c

a proven

gas

separ._~ted

2.0% O V - I 0 1 ,

was

to

quality.

was

destil]ate

and of

and

5710A

gas

95%

preparation

A Hewlett-Packard

oven

using

in

month

Jn the

in3ector

Germany)

prepared

diazomethane/ether

p~ecautions

wit]]

was

mixed

hydroxide

PFTE-lined

compounds

West

5 g N-methyl-N-nitroso-p-toluenesu]fonamide

2.5

used

reagent-grade

followed

added

not

of

Haen,

was

with

were

de

contamination. solution

solvents

(Reidel

the

condensate

extracted cap.

After

neutral

aqueous

concentrated

a method

and

phase

sulfuric

ca

was

acid,

1185

and

then

extracted

combined which

ether

I g Na2SO 4 had

dried

ether

acids

methylated

(7))

with

phases

and

at r o o m

extract

200

volume

was

ul of

the

was

the

water

of m o n o - , as

tested

occurred

the

performed

were

di-,

run

~I u s i n g

diethyl

2 ~i of t h e peak

of t h e

sample

the

organic

10 m i n u t e s

of N 2 gas.

The

ether.

limits.

were

Standard

analyzed

in the

Bromoacetic

rejected

as

acid

it a l s o

acids

Hewlett-Packard

to t h o s e

of

by c a r e f u l l y

chloroacetic

on t h e

heights

to

as a c a t a l y s t

standing off

efficiency. later

the

the

tube

portion

stream

acids

but w a s

test

acts

detection

extraction

Quantification

comparing

driven

to e s t a b l i s h

and

(which

a gentle

fresh

standard~

A 2 ml

After

was

trichloroacetic

to c h e c k

samples.

and

200

and

internal

by i n j e c t i n g

chromatograph

solution.

centrifugation,

conical

tube,

~i m e t h a n o l

diazomethane

to

After

agent.

to a t h i r d

200

to 2 ml u s i n g

samples

in t h e

of

ether.

to a s e c o n d

a drying

diazomethane

blanks

as a n

as

transferred

solvent

solutions same way

added

excess

readjusted

diethyl

transferred

by a d d i t i o n

Destilled

was

been

temperature,

concentrating

3 x 3 ml

were

was gas

of a r e f e r e n c e

standard.

As

there

were

unidentified sample

was

peaks

taken

samples

were

carried

out

were

N 2 gas.

the

was

to 0.8

The

volume

was

to

then

that

the

using

I ml

then

as t h e

with

adjusted

to

of

250 ml.

combined

volume due

the

ether using

sulfuric

to the After

500

acid.

with

2 x 2 ml,

were

again

to m e t h y l a t i o n ~I p r i o r

with

2),

the

stream

10 ml,

and

organic I x

and

(ca 200

a gentle

over

was

volumes

extracts

water,

then

4 Bor~s

Extraction ether

presence

The

of

a larger

to

the

I ml, pH

acids

were

I ml d i e t h y l

Na2SO 4 and

diazomethane. analysis.

of

the

of e t h a n o l

concentration

dried

to G C - M S

number

from

approached

2 ml d o u b l y - d e s t i l l e d

extracts

prior

figure

concentrated

equipment.

by s h a k i n g

ether

The

a large

volumes

scaling-up

dramatically,

sampling

(see

volume by

solvent

concentrated

ether

combined

concentrated

funnel.

acids

Condensate

a total

Na2SO 4 and

diluted

into

chromatogram

previously

decreased of

chloroacetic

analysis.

to y i e l d

noted

rate

re-extracted ether.

over

rinsing

solvent

adjusted

gas

in a s e p a r a t o r y

It w a s

the

in t h e

pooled

dried

evaporation from

to the

for G C - M S

as d e s c r i b e d

extracting ml)

in a d d i t i o n

The

final

186

F i g u r e 2 - G a s c h r o m a t o g r a m of m e t h y l a t e d h a l o g e n a t e d o r g a n i c a c i d s in s a m p l e iI f r o m the m u n i c i p a l i n c i n e r a t o r at B o r ~ s , S w e d e n . T h e GC c o l u m n (2 m g l a s s , 2 m m i.d.) w a s p a c k e d w i t h 20% O V - 1 0 1 , 9.1% C a r b o w a x 1500 o n C h r o m o s o ~ b W, 8 0 / ~ 0 0 m e s h . T h e GC o v e n w a s t e m p e r a t u r e p r o g r a m m e d f r o m 60vC to 1 7 0 - C at 4 ° C / m i n u t e .

<9 O

O O t~ t)

2rD

<)

0 0 U

0

U

r~

U o

4J D~ o 43 C~3

0 0 U

0 0 0

!

|

%

8

J

8

6

4

/

w

time (minutes)

16

14

12

1{)

;~

'0

Results

The

efficiency

tested

using

of t h e m e t h o d

destilled

KH2PO4/Na2HPO 4 buffer) ~g/ml

di-

and

58% to 98% chloroacetic

in e x t r a c t i n g

water

(buffered

spiked

trichloroacetic

(see T a b l e acid,

2).

The

probably

with

the

to pH 7 u s i n g

1.8 u g / m l The

lowest

recoveries

to

losses

percent

in t h e

acids

a 0.025

chloroacetic

acids.

due

chloroacetic

were

M

acid

recoveries

and

0.18

ranged

from

obtained

evaporation

was

with steps.

1187

Table

2. P e r c e n t

Chloroacetic

recoveries

of the c h l o r o a c e t i c

acid

Recovery Trial

monochloroacetic dichloroacetic

acid

acid

trichloroacetic acid

Chlorinated BorAs

acetic

municipal

corrected

be o b s e r v e d the

levels

has

trapped

Trial

61%

93%

87%

83%

81%

98%

87%

equipment

total

presented

in f i g u r e

3. T w e n t y - o n e

identified,

a given compound

refers

The a c t u a l

g i v e n p e a k could

Chlorinated

a c e t i c acids and e i t h e r

in t r a p p i n g

chlorinated

filter.

Thus

organic

e x t e n t they are

the

levels

presented

a c e t i c acids w e r e also

of a c o m b i n e d

condensate

sample

from

Sweden.

different

listed

c o n t a i n two or m o r e

b e n z o i c and b e n z e n e d i c a r b o x y l i c

of the

acids

is

of i s o m e r s

in the total

p r e s e n t could

isomers

sample

o r g a n i c acids

4. The n u m b e r

of peaks

of i s o m e r s

condensate

halogenated

in T a b l e

to the n u m b e r number

could

It s h o u l d be noted t h a t

ion c h r o m a t o g r a m of the c o m b i n e d

were t e n t a t i v e l y

chromatogram.

or HCI.

Chlorinated

at Ume~,

were

2. No d i r e c t c o r r e l a t i o n

and it is not k n o w n to w h a t

or by the XAD-2

from the

in e x t r a c t i o n and c o n c e n t r a t i o n

in Table

in a p r e l i m i n a r y a n a l y s i s

The G C - M S

forms.

losses

samples

concentrations

of the c h l o r i n a t e d

of the s a m p l i n g

incinerator

of the

3). The

aromatics

h e r e are at best a p p r o x i m a t i v e .

the m u n i c i p a l

in all

(see T a b l e

levels

not been tested,

identified

Mean

89%

of the c h l o r i n a t e d

on p a r t i c u l a t e s

3

78%

acids w e r e p r e s e n t

the

Trial 63%

incinerator

between

2

63%

percent recoveries

the e f f i c i e n c y acids

I

58%

for the a b o v e - m e n t i o n e d

u s i n g the m e a n

acids.

for

ion

be higher,

as a

same compound.

are the d o m i n a t i n g

In the case of the chloromethyoxybenzoic acids and the c h l o r o -

methoxybenzenedicarboxylic

acids,

it is i m p o s s i b l e

to say if the m e t h o x y

g r o u p was o r i g i n a l l y a h y d r o x y g r o u p prior to t r e a t m e n t w i t h diazomethane. agent.

This

The

carboxylic However,

is one d r a w b a c k

same acids

is true groups

the a u t h o r s

in u s i n g d i a z o m e t h a n e

for the d i c a r b o x y l i c could h a v e o r i g i n a l l y

acids,

been a m e t h y l

feel that the d i c a r b o x y l i c

study e x i s t e d as such in the s m o k e the d e c o m p o s i t i o n of p h t h a l a t e s

as the d e r i v a t i z i n g as one of the

acids

stack emissions,

ester.

identified

arising

in h o u s e h o l d w a s t e d u r i n g

in this

in part

from

incineration.

188

Table

3. C o n c e n t r a t i o n s

of c h l o r i n a t e d

the m u n i c i p a l

Concentration

Sample

chloroacetic C12

C1

incinerator

of

acetic

acids

in flue gases

at Bor~s.

Concentration,

acids, C1 3

3"

wq/m

summa

[ chloro-

pg/m 3

[ chloro-

benzene

phenol

HCI (mg/m 3 )

3

3.2

1.3

0.37

4.9

61

190

9

3.2

1.3

0.94

5.4

164

86

270

10

4.8

4.6

1.8

11

55

38

1000

11

7.8

5.7

3.7

17

40

33

34

*flue

gas v o l u m e s

normalized

to

from

10 % C02,

O°C,

1100

100 k i l o p a s c a l

pressure.

F i g u r e 3 - Total ion c h r o m a t o g r a m of m e t h y l a t e d o r g a n i c acids from the GC-MS a n a l y s i s of the c o m b i n e d c o n d e n s a t e samples from the Bor&s m u n i c i p a l i n c i n e r a t o r . Peak n u m b e r s c o r r e s p o n d to the c o m p o u n d s listed in T a b l e s 4 & 5. C a p i l l a r y column: 25 m DB-I (0.32 m m i.d., 0.25 tam film thickness) • o b o n d e d fused sillca, t e m p e r a t u r e p r o g r a m m e d from 20 C (one m i n u t e hold) to 50°C at 1 5 ° C / m i n u t e , then to 280°C at 5°C/minute.

2,6-bis(l,l-dimethylethyl)-4methylphenol

24

25

lO

\

13

25

14114 16 2

1

4 22

14 T

i

500 8:20

'1

r

r

20

r

I

10061 I6:40

15610 T5:00

20~£I 33:20

2500 4 ! : 4~i

1189

Table 4 - Halogenated organic acids identified in the flue gases from the Bor~s municipal incinerator. NO.

Name

NO. of isomers identified

Chemical structure

Molecular weight

I chloroacetic acid

I

CI-CH2-C-OH

94

2 dichloroacetic acid

I

CI2-CH-C-OH

128

3

trichloroacetic acid

I

CI3-C-C-OH

162

4

bromoacetic acid

I

Br-CH2-~-OH

138

q

5

dibromoacetic acid

I

6

chlorobutenedioic acid,ethyl ester

2

HO-C-CH=C -~-O-C2H 5

178

7 dichlorobutenedioic acid

I

0 C1 C1 O HO-~-~ =~ - ~ - o .

184

8

dichlorobutenedioic acid,ethyl ester

I

HO-~-~ =C -6-O-C2H 5

9

chlorobenzoic acid

2

dichlorobenzoic acid

4

10

Br2-CH~C-OH

216

Cl 9

o

9 Cl cl

o

212 156

COOH C l n ~

190

11

trichlorobenzoic acid

2

224

12

tetrachlorobenzoic acid

2

258

~3

chlorobenzenedicarboxylic acid

2

2OO

14

dichlorobenzenedicarboxylic acid

3

15

trichlorobenzendicarboxylic acid

2

n ~ (

234 COOH)2

Cl 16

tetrachlorobenzenedicarboxylic acid

I

17

bromochlorobenzenedicarboxylic acid

1

268

302 B r ~ (

334

C1

COOH)2 COOH

18

trichloromethoxybenzoic acid C I ~ O C H

19

tetrachloromethoxybenzoic acid

20

dichloromethoxybenzenedicarboxylic acid I

I

254 288

CO°HI2 C12

21

3

~

264

XOCH3

4 ~ C O O H

tetrachlorobenzenedicarboxylic acid, ethyl ester

330 C1

C-O-C2H5

119o

Table 5.

No.

Other organlc compounds identified in the flue gases from the BorAs munlcipal incinerator.

Name

No. of isomers identified

Chemlcal structure

Molecular weight

22

butanedioic acid

I

HOOC-(CH2)2-COOH

i18

23

butanedioic acid, ethyl ester

~

HOOC-(CH2)2-C-O-C2H 5

24

benzoic acld

I

COOH / ~

122

25

benzenedicarboaylic acid

2

LI\

166

?

146

~(COOH) 2 OH 26

pentachlorophenol

~

cICI~Cic1

264

C1

Other, Table

non-halogenated 5.

It

is

halogenated formed

by

acid,

in

GC-MS

the

detected to

the

acids

which

are

analysis

among

have

BHT.

It

extraction samples

peak is

present the

3,9,10

combining

them,

next

to

ion

chromatogram

significant

a

ethanol/water

for

of

detected

the

ethanol

amount

leaving

the

phase

(see

could

benzoic the

in

total

in

with

this

likewise

and

the are

incinerator.

along

identified and

the

to

latter

the

solvent

study, be

has

benzenedicarboxylic

ion

chromatogram.

aliphatic

airborne

and

These aromatic

1-dimethylethyl)-4-methylphenol,

also

An

to

500

HI,

peak

larger

majority

of

all

the

due

to

the had

BHT

onto

the

behind

the

the

BorAs

GC-MS the

taken

acids

fortunate in

in

presence

volume

known

by

the

others

(8).

in

the

tubes)

organic

the

used

analyze

test

condensate

which the

in

ether

to

injecting

re-extract

ether,

analysis).

and

masked However,

the to

diethyl

attempt

methylated

minutes.

of

the

and

BHT

in

in

earlier

been

a precursor

matter

necessary

(5 ml)

elutes

the

in

particulate

acids.

several

of

in

former

presented

precursors

the

a preservative

as

are

that

not

in

are

non-halogenated

(extracted

it w a s

these

form

The

peaks

identified

suggesting

(4)

other

concentrating

amount

smaller

consequence

as

impossible

analysis,

as been

11

was

acids.

organic

and

was

into

thus

2,6-bis(1,

of

of

emissions

largest

is

that

and

well

previously

largest

GC-MS

the

also

4,

methylated

acetic

as

note

Table

its

incinerator

acids,

to in

acids

halogenation in

halogenated

acids,

as

listed

successive

in

aromatic

The

interesting

acids

Acetic

organic

total of

a

for

back

119

Extraction

of t h e

removed

the

in t h e

GC-MS

and

neutral

a small

phenols.

and

Other

of

at pH

phenolic

chromatogram, amount

in the G C - M S

with

7 with

compounds, the

aliphatic

and

aromatic

but

the

ether

of

carboxylic

acidic acids

spectral

by

their

absence

the a f o r e - m e n t i o n e d

the m o s t

mass

effectively

as w i t n e s s e d

exception

pentachlorophenol,

chromatogram,

diethyl

data

of

the

were were

BHT

chloro-

also

present

insufficient

identification.

to p e r m i t

Positive

condensate

ion

confirmed

chemical

ionization

the m o l e c u l a r

25

(see t a b l e s

of

the

other

4 and

GC-MS,

weights

5).

High

of

using

compounds

background

methane 2,

3,

6,

as

a reagent

9,

22,

unfortunately

23,

masked

gas,

24,

the

and

spectra

compounds.

Conclusions

Twenty-one the

different

first

stack

time

emissions

previously

dioic

acid,

manufactured likely

that

halogenated

Further

and

or

in s m o k e

in c o m m o n

of t h e

stack

being

the

halogenated

significant

formed

in t h e

are

needed

emissions

the a m o u n t s

emitted

extent

they

are

assess

the

to

been

acids

extent

the

reference

effects

acids,

are

in the

they

than

of

and

It a p p e a r s

aquatic

may

have

non-

gases.

these

compounds

accurately

if a n d

and

chloro-

to be

as t h e i r

flue

identity

have

pulpmill

known

process,

for

in s m o k e

chlorobutene-

Other

2) d e t e r m i n e

in t e r r e s t r i a l

kraft

in S w e d e n .

compounds

detected

compounds

from

10).

detected

environment,

negative

9,

incineration

I) c o n f i r m

using

to t h e

distributed

potential

also

(6,

of t h e m

identified

Similar

liquors

organic

to a n y

have

many

been

chloroacetic

acid

are

precursors

have

bleach

used

they

acids,

incinerator.

in s p e n t

a dichlorobenzoic

none

studies

organic samples,

a municipal

reported

those

acids,

acetic

from

been

industries,

halogenated

in e n v i r o n m e n t a l

measure

to w h a t

ecosystems,

on l i v i n g

and

:3)

organisms.

Acknowledqements

The

authors

Folke

Lindskog

like

for

from

to t h a n k

help

for a s s i s t a n c e

preparation grant

would

Osterberg

Samuelsson

in d e v e l o p m e n t

of t h e m a n u s c r i p t . the N a t i o n a l

Ulla

in i n t e r p r e t a t i o n

Swedish

This

of

of t h e

study

was

Environmental

for p r o p o s i n g

the mass

this

spectra,

and

method

and

analytical supported Protection

financially Board.

study, Anne

by a

1192

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R.

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