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PCDD/F mass balance of a recycling paper mill

Conference Paper · September 1992

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Ludwig Gruber Helmut Santl

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 sou
Session 10

PCDD/F mass balance of a receding paper mill

A. Bichlmaier^, L. Gruber^, E. Stohrer^, O. Tillmann^ and H. Santl^

A

Fraunhofer-Institute for Food Technology and Packaging, 8000 Munchen 50, Germany
Steinbeis Temming Papier GmbH, 7121 Gemmrigheim, Germany

Introduction

The possibility of the formation of polychlorinated dibenzofurans (PCDFs) and

polychlorinated dibenzodioxins (PCDDs) in the pulp industry is a well known fact. In spite
of some very detailed studies in the field of pulp bleaching there is still no systematic
investigation about the input, formation and fate of PCDD/F in paper mills. In a first step
all parts of the production process from the raw material to the final product of a recycling
paper mill were analysed.

f Materials and Methods

i The investigation was composed of two parts.

L In order to gain a first survey about the input and the fate of PCDD/F in the paper
mill, samples were taken during one week of production. Intending to register the whole
' production process with its inputs and outputs, 51 samples had to be taken, including
sample mixtures from the main mass fluxes. In a first screening seven samples and one
I mixture of the deinking chemicals were analysed.
' In the second part of the investigation random samples were collected in the
I chronological order of the production process. These samples especially were used to
calculate the PCDD/F balance resulting from the deinking process and to verify the results
of the first part of the investigation.
All samples were prepared according to a standard method. The samples were spiked
with a mixture of fifteen carbon-13 labeled PCDD/F prior to extraction. Liquid-liquid
partition with dichloromethane for the water samples and Soxhiet extraction with
ethanol/water for solid samples were carried out. The extracts were purified by an extensive
multistep cleanup procedure including superactive basic aluminia, silica/sulfuric acid,
silica/potassium hydroxide and a carbon/celite column. The analysis were carried out by
HRGC/HRMS using a DB-5 fused-silica capillary column, coupled with a Finnigan MAT
90 mass spectrometer with electronic impact ionization. For each congener at least two
isotope masses were measured.

Organohalogen Compounds (1992) Volume 9

25
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Session 10
Results and Discussion

The final results of both samplings are summarized in Figure 1. As expected, the
highest amounts of PCDD/F were found in the deinking sludge (44.37 ng I-Teq/kg dw and
24.82 ng I-Teq/kg dw) and in the sludge from the effluent treatment plant (11.01 ng I-
Teq/kg dw). The levels of the waste water and the circulating water are very low, 0.055
and 0.013 ng I-Teq/l respectively. In both samplings significant lower PCDD/F
concentrations were determined in the outgoing: recycled paper ( 1.54 and 1.12 ng I-Teq/kg
dw) compared to the input of the waste paper (4.44 and 2.96 ng I-Teq/kg dw). A reduction
of the PCDD/F levels by a factor of about 2.7 lo 2.9 has been observed.

1 WASTEPAPEF! 1

4 4^ <n\ 1 9.<J6 ^h1

1 j 1
^'* ^ 1
1
1

! DEINKING- j PULPER i CIRCULATING 1

1

1
1 CHEMICALS i
I !
i WATER 1
1
1
1
1 •
1 1 t 0.013 (a)
n.d. (a)
DEINKING-
1 SYSTEM
- \
1
/
DEINKING- i
» WASTEWATER
SLUDGE i ECYCLED PUIJ 1 1
I
1.
L.
X 2 . 95 (a) 1.6J) (b) / 0.055 (a)
4^\.37 (a) 24.82 ( b)

DISPERGER /

iT
1 EFFLUENT TREAT-!
RAWPAPER AFER j 1^ MENT PLANT: i
PRESS SECTION PM 4
SLUDGE j
1. r

1.40 (b)
r
RECYCLE!Dj
1 11.01 (a)

PAPER
i 54 (o) 1.12 (b)

Figure 1: Scheme of the recycling paper mill

All results are given in ng I-Teq/kg.
' ) Results from first sampling in July 91.
") Results from second sampling in December 91.

Organohalogen Compounds (1992) Volume 9

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Session 10

The partition of the PCDD/F in the paper mill can be calculated including the mass
fluxes. The waste paper had a 99,5% share in the PCDD/F-mput. The main output comes
from the deinking sludge (about 60%) and the recycled paper (about 30%). In this case the
effluent treatment sludge had not been considerated, because this output was already
included ui the effluents of the paper mUl, A formation of PCDD/F could not be observed.
The typical PCDD/F pattem of some solid samples are presented in Figure 2.
Mainly low concentrations of some TCDFs, some non-2378 substituted HxCDDs and
higher levels of the HpCDDs and the OCDD could be found. The PCDD/F pattem of all
samples correspond with one another, as well as the ratios between the main compounds are
nearly constant in all solid samples. This confirmed the thesis, that no relevant amounts of
PCDD/F are formed in the production process or introduced by process chemicals which
have not been analysed in the first screening.

250a

200O

ll 1.
^ i5oa

"1" 1000

5oa IL
1 ll. r ueinking-biudge ^^^l'd^
f w z s t e Paper Input 7/91
jMKH^j ll^lM§ll^i^Bftl$fl0ltl^MI^Mlll^l^
1 1 1 1 1 1 1 1 1 1 1 1 i ,
0 /c^/c:?/ t
ur... . -h-aper input
waste .
IC=II!::DIC:::I(LJICO(CJIU(I=I(C:D(Q^ Recyciea raper i.^/ai
i.i/ai

CO oo 03 oo 1 1 1 1 1 1 1
D ; C ; E ; C ; O O O I O 3 O O O O O O O O
c^ rsi c-M OJ t o 1—. r-O CO !--> l o ;.-,
1 1 PO ro c*N -<r CN .td- CN
O O — — c O ^ c C V l i
^ ZZ o -" O -^ o

Figure 2: PCDD/F pattem of samples from a recycling paper mill

The results of the second sampling showed lower values of PCDD/F (Figure 1).
However the results of the first sampling were verified, regarding the detected PCDD/F
pattem (Figure 2) and the PCDD/F partition in the recycling paper mill. With these results
a simplified PCDD/F balance of the deinking process was calculated. The PCDD/F-input in
the deinking plant results from the waste paper in a share of 99.5%, according to the first
results. 96% of the PCDD/F-output consisted of the deinking sludge and the recycled pulp.
Therefore only this three samples were used for balancing. The results are shown in table 1.
The PCDD/F mass balance isfijlfiUedvery well.

27
Organohalogen Compounds (1992) Volume 9
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Session 10

Input Output Mass balance

waste recycled deinking output/
paper paper sludge input
(HR I-Teq/h) (ixg I-Teq/h) (ixg I-Teq/h) (%)
BGA-Teq 19.4 9.1 13.5 116

I-Teq 18.4 9.2 11.8 114

Table 1: PCDD/F balance of the deinking process

Refering to the results, the following conclusions can be drawn:

The PCDD/F-input in a recycling papijr mill comes from the waste paper. The main
output is in the deinking sludge.
The concentrations of PCDD/F in the recycled paper are about three times lower than
the PCDD/F concentrations in the corresponding waste paper.
No measurable amounts of PCDD/F are: formed during the deinking or the papermaking
prozess.

Acknowledgement

This study is part of the BMFT-project Nr.0lZV9004 'Investigation of the formation

and fate of toxic organochlorine substances in the pulp and paper industry'. The authors
would like to thank the Bundesministerium fiir Forschung und Technologic (BMFT) and the
Verband Deutscher Papierfabriken (VDP) for their financial support.

Organohalogen Compounds (1992) 28 Volume 9

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