Sampling of polychlorinated dibenzofurans (PCDF) and dibenzo(p)dioxins (PCDD) in emissions from combustion facilities using an adsorption method

Chemosphere, Voi.24, No.ll, pp 1563-D72, 1992 Printed in Great Britain

0045-6535/92 $5.00 + 0.00 Pergamon Press Ltd.

SAMPLING OF POLYCItLORINATED DIBENZOFURANS (PCDI0 AND DIBENZO(P)DIOXINS (PCDD) IN EMISSIONS FROM COMBUSTION FACILITIES USING AN ADSORI~ION M E T I t O D W e r n e r F u n c k e and H e i n z L i n n e m a n n

GfA - Gesellschaftffir Arbeitsplatz- und UmweltanalytikmbH, Otto-Hahn-StraBe 22, D - 4400 Mfinster-Roxel,Fed. Rep. of Germany Keywords: PCDD, PCDF, sampling, adsorption method

Abstract A sampling method for PCDF/D in emissions from combustion and other industrial facilities is presented in which these substances are deposited in one collection unit consisting of a combination of quartz wool and a polymeric adsorbent (pretreated XAD-2 resin). In combination with a cooled probe, this sampling method can be used for flue gas at temperatures up to more than 1,000 °C, with dust contents up to more than I g/m 3 and water contents of more than

300

g/m 3.

Performance

characteristics

referring

relative

standard

deviations

from

parallel determinations and comparison with other sampling methods are presented for PCDF/D flue gas concentrations between 2 and 0.02 ng

(TE)/m3 (Toxicity equivalent according to

NATO/CCMS).

I

Introduction

In t h e

Federal

ling

methods

loped the

and

for

in

these

the

described given The

sampling

minate

or

mentioned this

in

in

method

time

facilities

series 1 -

at

part

for PCDF/D

2,

it w a s at

from

4 of

this

guideline

concentrations

here

flue

gas

>

1 ng

was

in

than

planned

1988 250

1563

samp-

were

preliminary

deve-

drafts

characteristics

show

good

( T E ) / m 3.

for pre-

comparability For

the

characteristics

and

in

1987

of

the

method

are

with

of

i00

the

aim

VDI-guideline

optimized

samplings

concentrations

[5,6].

different

also

( T E ) / m 3.

disadvantages

used

more

series

of

performance

of < 0.i ng

the

first in

The

as

four

facilities

performance

presented

tested

combustion

[I - 4].

corresponding

It was

last years

3499

minimize

PCDF/D

gas

the

exist

concentrations

least

above.

flue

over

descriptions

PCDF/D

device

at

Germany

The

parts

methods

of

PCDF/D

tested.

VDI-guideline

sented of

Republic

at to

until

1991.

different <

0.005

to

eli-

methods During

combustion ng

(TE)/m 3

1564

2

Expct'imenlal

2.1

Sampling Equipment

The sampling

equipment

which

according to VDI-guideline

allows

isokinetic

collection

of flue gas dusts

2066, part 1 [7], is shown in figure I.

The equipment contains the following parts: a) Probe: tures PCDF/D ted

nozzle,

> 80

elbow

°C double

collecting

XAD-2,

flexible

phase:

D0-frit;

spherical

with glass

support

tube

to

joints;

via

gas

glass

cooler

tubes

for

wool, with

extensive

b)

pretreagastight,

removal

of

d) gas transporting system with volume meter.

Sampling

The PCDF/D-sampling meter

and

concerning

determination

of

isokinetic

flue

gas

suction,

tube

spiked

is cleaned

with

or

13C-labelied

> 80 °C to over 1,000

renewed,

°C a water-chilled

at flue

gas temperatures

used.

In case

of

ries.

Dependent

tection

flue

gas

on flue

of < 80

dust

is recommended

is

drying tower,

realized

pretreated

For

flue

gas

XAD-2

suction tube is used °C an uncooled

concentrations

limit for PCDF/D-congeners

PCDF/D

to

of

is used,

temperatures

> 1 g/m 3 a

concentration

of

(according to

suction tube

can be

larger quartz

or a glass cyclone has to be connected

gas velocity,

gas-

according

(ca. 4 mm ID) inside the suc-

especially

PCDF/D-standard(s).

[3]);

wool cartridge

and

pump,

parameters

[2,7]. Prior to each sampling the glass insert tion

at flue gas tempera-

cooling of the probe;

stuffed with quartz

probe c)

inserts;

for water

glass-cartridge

connection ground

flue gas humidity;

2.2

(titanium)

cased

in se-

and desired

de-

a suction volume flow of 0.5 to 2 m3/h is

adjusted.

2.3

Work-up and Analysis

Usually only the glass cartridge, from the sampling. ded

in

the

The glass

work-up

if

dust

usually avoided or minimized the

condensate

washed

which

results

into the glass

further clean-up

results

insert inside the suction tube is rarely includepositions

are

visible.

Such

depositions

by using a glass tube with suitable from

cartridge.

and analysis

filled with quartz wool and XAD-2,

cooling

the

The extraction

is realized

tube,

by which

of the matrices

analogous

are

ID, and by the

dust

is

as well

as

to the descriptions

gi-

ven in [2]. At a sampling volume of 10 m 3 and application of a HRGC/HRMS-system

(e.g. VG

AutoSpec)

-

for

e.g.

ng/m 3 is reached.

2,3,7,8-TetraCDD,

This way TE-values

a

detection

limit

of

0.0005

0.001

of 0.01 ng/m 3 can be determined without

1565

r,

v

r"

o

'o

r" -,4 .,-I

~

. ~ 1

.-4

@

¢" -I~ '~J ~:1~>~

o o o . ~ , ~ , ~ 4.~ . ~ -,..~

~., ~:~ ,~ q.~ ~t

o /t

t.-,.

1566

being

influenced

blank values

decisively

by

not

can be kept below

detected

0.001

ng

PCDF/D-congeners.

The

PCDF/D

(TE)/m 3 (referred to i0 m 3 sampling

volume). If 13C-I,2,3,4-TetraCDD

is used as standard for spiking the XAD-2, mean reco-

very rates of usually 90 % are observed.

This is higher than for other samp-

ling methods used so far [i - 3].

Results and Discussion

3.1

PCDF/D Dispersion

To verify

the PCDF/D

tial PCDF/D cartridge);

inside c)

back-up

each

in the sampling

from XAD-2

the

probe;

condensate

behind

XAD-2

cartridge

collection

centration

dispersion

break-through

glass-insert d)

in the Sampling Device

phase

level

shown

of ca.

b)

in

5 ng

figure

unit

unit

condenser 2

(quartz

(cooled

unit).

are

and to check poten-

phases were analysed:

adsorption

adsorption

(behind

device

the following

flue gas;

The PCDF/D

referred

(TE)/m 3, a suction

to

a)

wool/XAD-2 20

°C);

portions

a

PCDF/D

rate of 2 m3/h,

in

con-

a sampling

volume of ca. I0 m 3 and a XAD-2 temperature of 20 °C. The PCDF/D-portion deposited tal

PCDF/D.

adsorption

The

performance

case of OctaCDF. backup

XAD-2

in the filter/adsorption

differentiation with

homologeous

increasing

The additional

cartridge)

of

chlorination

collection phases

contain

only

very

unit is > 99 % for to-

groups

low

shows

order

down

(probe tube, and

a

decay

to

95

in

%

condensate

therefore

in +

irrelevant

PCDF/D-portions which slightly increase with degree of chlorination.

3.2

Standard Deviations

from Parallel Determinations

[5, 8] The relative lysis) in

case

PCDF/D

standard

from parallel of

PCDF/D

groups

for the complete method

determinations concentrations

concentrations

homologeous

deviations

around

and single

0.02

shown of

2

ng

congeners

in table

ng

i and 2, are about

(TE)/m 3 and

(TE)/m 3.

(sampling and ana-

The

slightly

standard

are higher;

this

i0 %

higher

deviations

at for

is especially evi-

dent for the lower PCDF/D concentration range. It

has

errors sulting

to

be

noted

from sampling, from

be excluded.

that

standard

clean-up

local or temporary

deviations

and analysis,

do

not

only

include

but also systematic

non-homogeneities

random

errors re-

in the stack which cannot

1567

PCDF/D-Percentage (Differentiated by Homologeous Groups) in Probe Tube, Adsorption Unit and Condensate + Backup XAD-2 Cartridge. The Total of the PCDF/D Concentrations in all Collection Phases is Equivalent to i00 %; Mean Values and Ranges out of 6 Samplings in the PCDF/D Concentration Range of 5 ng TE)/m 3

Figure 2:

54,54 3.5

PCDF/D- P ~ T I ~ (~) IN GLASS- TUBEINSIOE~OBE

3

2.52 1,5

i

10.5-

~

0

'.

"

'

"

PCDF/D- PORTION(%)

INADSORPTIONUNIT

I00 l 99~

9a! 9796. 95.

94. 93. 92

91 90,

PCOF/D- PORTION(X) IN CONDENSATE(AFTERADSORBENT) AND IN BACK-UPXAD-2 CARTRIDGE

109. 8

7 6 5 4

O ' ~ '

•

•

i

-- ,--L,. . . . . . (T4COO"PSCDD H6CDOH/CO00CDO

i

T4,COFPSCOFHBCOF"H7COFOCDF

The

standard

levels are [i

-

deviations,

documented

in the same range

for

corresponding

as specified

PCDF/D

4-8 COF/O

concentration

for other PCDF/D sampling

methods

3].

C o m p a r i s o n M e a s u r e m e n t s with a Known S a m p l i n g M e t h o d

3.3

The

sampling

[2]

at

method

relatively

presented high

The best comparability

and

here was compared

relatively

is shown

low PCDF/D

especially

of ca. 1 ng (TE)/m 3 (see figure 3).

to the method flue

for higher

gas

PCDF/D

described

in

concentrations. concentrations

1568

In case 4),

of

lower

partly

HeptaCDF

PCDF/D

higher

concentrations

deviations

and TetraCDD

are

are

of

ca.

observed.

not real

0.02

The

because

ng

(TE)/m 3

highest

the totals

the

are considerably

in-

As mentioned earlier,

geneities

have

the

estimation

thods.

flue

of

gas

the

The relative

channel

concentration

PCDF/D

to

be taken

differences

concentration

4

PCDF/D concentration

observed

differences

levels

possible non-homo-

into consideration for

shown

4 are in the range of the relative standard deviations at corresponding

figure for

fluenced by not detected congeners. in the

(see

deviations

the

for

two

in figures

me-

3 and

for the two methods,

(see tables i, 2 and [2, 5]).

Conclusion

The results

presented

here show that the new sampling method

for the determination This

includes

of PCDF/D

PCDF/D

in flue gas of e.g.

concentration

levels

of

0.02

the verification

of the threshold value of 0.i ng

the 17. BImSchV

[9].

the

sampling

equipment

equipment

can

be

almost

network

in dust sampling techniques

measurements

are

following

measurement

equipment

after

solvents)

is

eliminated

unnecessary;

in

the

contact

glass cartridge; case

of

the

adsorbent, dust with

g)

with

and

the

e)

in

[i - 4],

advantages:

a) the

(up to

1,000

(over i g/m 3) of the flue at the sampling

location;

c) the requirements

measurements;

minutes;

sampling

possible

value

of

gas

extensive

location

secondary the

are

methods

solution), resin;

cartridge

13C-PCDF/D-standard)

described

temperature

d)

limited

(probe

only in

with

can

one

case

is

to

the

sent

probe

filter off

by

of

for a

of

the

inflammable is

largely

minimized glass

because

tube

and

the

collection matrices

dust

collection

dust

be

tube,

the

with

contamination

equipment

for

exchange

cleaning

(e.g.

in contrast to up to 5 different

XAD-2

glass

only

the

flue

conventional

washing

filter

here;

f)

blank

dust

assures

(including dust filter and XAD-2 resin)

requires at

to

(TE)/m 3 which

following the

is sufficient;

comparable

sampling

and

the of

of the sampling equipment

glass tube and glass cartridge

surfaces

here has

independent

(over 300 g/m 3) and dust content

simple handling

knowledge

ng

facilities.

(TE)/m 3 in accordance with

to at least one method

presented

used

°c), water content gas; b)

Compared

is appropriate

combustion

filter,

matrix

tube)

(cartridge

has

to

and

adsorbent

the

analytical

be

with

analysed

(e.g.

spiked

laboratory;

spiking of the equipment at the sampling location is no longer necessary; costs for

for

the

sampling

costs

for

sampling

equipment

preparations

analysis

are

are

reduced

are

reduced as

relatively and

well,

collection phases have to be extracted.

due

low; to

because

i)

that only

time or

h)

requirements

sampling one

in

condensate,

in

costs; case

j) two

1569

Table

i:

Mean Values (~), A b s o l u t e and Relative the Complete Method from 8 Parallel Work-up and Analysis) at Relatively High

Parameter

I

s

i

Standard Deviation (s) of Determinations (Sampling, PCDF/D Concentrations

Srel

m

PCDF/PCDD Total TetraCDF Total PentacDF Total HexaCDF Total HeptaCDF OctaCDF Total Tetra- to OctaCDF 2378-TetraCDF 12378-/12348-PentacDF a 23478-PentaCDF 123478-/123479-HexaCDF a 123678-HexaCDF 123789-HexaCDF 234678-HexaCDF 1234678-HeptaCDF 1234789-HeptaCDF Total TetraCDD Total PentaCDD Total HexaCDD Total HeptaCDD OctaCDD Total Tetra- to OctaCDD 2378-TetraCDD 12378-PentaCDD 123478-HexaCDD 123678-HexaCDD 123789-HexaCDD 1234678-HeptaCDD Total Tetra- to OctaCDF/D TE (NATO/CCMS 1988)

ng/m 3

ng/m 3

40,7 27,0 12,1 4,0 0,6 84,4

3,6 3,3 1,1 0,5 0,3 7,1

9 12 9 13 50 8

8 8 8 8 5 8

0,17 0,30 0,19 0,17 0,18 0,04 0,06 0,38 0,06

ii ii 14 10 i0 25 8 13 29

8 8 8 8 8 8 8 8 8

0,4 0,6 0,5 0,3 0,4 1,6

ii 15 16 13 13 i0

8 8 8 8 8 8

0,03 0,06 0,04 0,03 0,03 0,12

ii I0 19 11 8 10

8 8 8 8 8 8

8

8

i0

8

1,54 2,63 1,32 1,71 1,74 0,16 0,71 3,04 0,21 3,6 3,9 3,1 2,4 3,0 16,1 0,28 0,62 0,21 0,28 0,40 1,26 100,4 2,11

8,5 0,22

%

For totals and toxicity equivalents (TE} not detected congeners or homologeous groups are not included a gaschromatographically not separable on SP 2331

1570

Table

2:

Mean Values (~), A b s o l u t e and Relative the Complete Method from 5 Parallel Work-up and Analysis) at Relatively Low

Standard Deviation (s) o f Determinations (Sampling, PCDF/D Concentrations

Parameter

~

s

PCDF/PCDD

ng/m 3

ng/m 3

%

Total TetraCDF Total PentacDF Total HexaCDF Total HeptaCDF OctaCDF Total Tetra- to OctaCDF

0,140 0,189 0,142 0,070 0,034 0,575

0,095 0,060 0,054 0,029 0,024 0,106

68 32 38 41 71 18

5 5 5 5 3 5

2378-TetraCDF 12378-/12348-PentaCDF a 23478-PentaCDF 123478-/123479-HexaCDF a 123678-HexaCDF 123789-HexaCDF 234678-HexaCDF 1234678-HeptaCDF 1234789-HeptaCDF

0,0122 0,0233 0,0119 0,0351 0,0162 0,0026 0,0069 0,0487 0,0051

0,0082 0,0099 0,0007 0,0131 0,0061 0,0006 0,0038 0,0194 0,0028

67 42 6 37 38 23 55 40 55

5 5 5 5 5 5 5 5 4

Total TetraCDD Total PentaCDD Total HexaCDD Total HeptaCDD OctaCDD Total Tetra- to OctaCDD

0,022 0,032 0,030 0,010 0,019 0,113

0,013 0,006 0,016 0,005 0,004 0,022

59 19 53 50 21 19

5 5 5 5 5 5

2378-TetraCDD 12378-PentaCDD 123478-HexaCDD 123678-HexaCDD 123789-HexaCDD 1234678-HeptaCDD

0,0025 0,0050 0,0020 0,0029 0,0021 0,0050

0,0015 0,0013 0,0012 0,0013 0,0017 0,0025

60 26 60 45 81 50

5 5 4 5 5 5

Total Tetra- to OctaCDF/D

0,688

0,096

14

5

TE (NATO/CCMS

0,0207

0,0022

11

5

1988}

Sre 1

For totals and toxicity equivalents (TE) not detected congeners or homologeous groups are not included a gaschromatographlcally not separable on SP 2331

1571

Figure 3:

Percentage Differences in P C D F / D C o n c e n t r a t i o n s determined w i t h the New M e t h o d (Set to i00 %) and the M e t h o d d e s c r i b e d in [2] at P C D F / D Flue Gas C o n t e n t s of ca. 1 ng (TE)/m 3. Mean V a l u e s and R a n g e s from 5 P a r a l l e l D e t e r m i n a t i o n s 50'

3020 10 0

II

• .,ll

'1 I1'11

,,.,.,ll,il=

I r

-10-20-30 -40 -50 T4COF" P5CDF H6CDF H7CDF OCDF

T4CDD

P5CDD

H6CDD

H7CDO

OCDD

4-8

CDF/D

Figure 4:

Percentage Differences in P C D F / D C o n c e n t r a t i o n s D e t e r m i n e d w i t h the N e w M e t h o d (Set to I00 %) and the M e t h o d D e s c r i b e d in [2] at P C D F / D Flue Gas C o n t e n t s of ca. 0.02 ng (TE)/m 3. M e a n V a l u e s and R a n g e s from 5 P a r a l l e l D e t e r m i n a t i o n s 100 80 604020 0

,,.= |

i

i

,

'i

-20 -40 -60-80-

-100 T4COF PSCDF H6COF H7CDF OCDF

T4CDD P5CDO HGCOD H7COD OCOD

4-8

cOr/o

1572

Finally

it has to be pointed out that not only PCDF/D but further,

relati-

vely unpolar substances of comparable volatility can be detected with this equipment as well: polybrominated dibenzofurans (PBDF), polybrominated dibenzo(p)dioxins (PBDD), polybrominated/-chlorinated dibenzofurans (PBCDF), polybrominated/-chlorinated dibenzo(p)-dioxins (PBCDD), trito decachlorinated

biphenyls

(Tri- to DecaCB),

(Penta- and HexaCBz),

penta- and hexachlorinated

tri- to pentachlorinated

polychlorinated naphthalines

phenols

benzenes

(Tri- to PentaCPh),

(PCN), polycyclic aromatic hydrocarbons

(PAH).

Acknowledgements We would like to thank the Ministerium fur Umwelt, Raumordnung und Landwirtschaft of North Rhine Westphalia for financial support and Dr. Br~ker of the Landesanstalt fur Immissionsschutz,

Essen,

for professional consultation du-

ring execution and development of this project.

L~erature [i]

VDI-guideline 3499, part 1 (draft), DUsseldorf,

[2]

VDI-guideline 3499, part 2 (preliminary draft), DUsseldorf,

1990

[3]

VDI-guideline 3499, part 3 (preliminary draft), DUsseldorf,

1990

[4]

VDI-guideline 3499, part 4 (preliminary draft), DUsseldorf,

1988

[5]

GfA-report schaft:

to

the

Ministerium

"Entwicklung

polychlorierten industrieller

fur

Umwelt,

1990

Raumordnung

eines vereinfachten Verfahrens

Dibenzofuranen

Feuerungsanlagen".

und

Dibenzo(p)dioxinen

This procedure

und

Landwirt-

zur Probenahme von

contains

in

Emissionen

a pending pa-

tent. [6]

W. Funcke and H. Linnemann: unpublished results.

[7]

VDI-guideline 2066, part i, DUsseldorf,

1975

[8]

VDI-guideline 2449, part i, DUsseldorf,

1970

[9]

"17.

Verordnung

zur

Durchfflhrung

(Verordnung Uber Verbrennungsanlagen Stoffe - 17. BImSchV)",

des

Bundes-Immissionsschutzgesetzes

fur Abf~lle und ~hnliche brennbare

Bundesgesetzblatt,

2545 (1990)

(Received in Germany 2 March 1992; accepted i0 April 1992)