Chemosphere,Vol. 30, No. 9, pp.

1805-1811, 1995
~ ) Pergamon Elsevier Science Ltd
0045-6535(95)00068-2 Pnnted in Great Britain
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DESTRUCTION OF PCDD AND PCDF

IN BLEACHED PULP BY CHLORINE DIOXIDE TREATMENT.

~ ~ ) , Nils G. Johansson2)and Christian Blom 2)

~)Eka Nobel, Research and Development, S-445 80 Bohus, Sweden

2)Eka Nobel Inc., 1519 Johnson Ferry Road, Marietta, GA, USA

(Received in Germany 7 December 1994; accepted15 February 1995)

ABSTRACT

Softwood pulp samples, containing polychlorinated dibenzo-p-dioxins and dibenzofurans (dioxins) were
treated with chlorine dioxide and analyzed, before and aftertreatment,for the contents of dioxins. Two
separate experiments were carried out under identicalbleaching conditions - similarto the elemental
chlorine free bleaching of kraftpulp. Each of the two experiments were duplicated,including the analytical
determination of the dioxin concentrations.In the firstexperiments the amount of dioxins in the chlorine
dioxide treatedpulp was found to be between 39 and 69 % of the values found in the originalpulp. In the
second experiments both the pulp as well as the effluentswere analyzed. The resultsfrom these duplications
proved to be consistent.For 2378-TCDD and 2378-TCDF, 56-63 were found in the pulp sample after
chlorine dioxide treatment. The vast majority was found in the pulp while the contributionfrom the aqueous
discharges was negligible.The conclusion is that the levels of the dioxins in the originalpulp decreased as a
result of the treatment of the pulp with chlorine dioxide. The results are significant since the results of the
experiments, including the analytical determinations, were highly reproducible.

INTRODUCTION

Various anthropogenic sources of polychorinated dibenzo-p-dioxins (PCDD) and polychlorinated

dibenzofurans (PCDF) emissions have been established, e.g. from incineration processes, chlorination of
natural waters and bleaching of pulp using (molecular) chlorine. On the other hand there are also natural
sources, ranging from forest fires to living cells - e.g. peroxidase enzymes (I). The precursors of the
PCDD/F may be chlorophenols but can also be chloride ions (2).

The PCDD/F profile, re. the distribution of the specific congeners, is regarded as typical for the individual
source. The use of molecular chlorine for bleaching pulp gives a very characteristic pattern of three
tetrachlorinated congeners, 2378-TCDD, 2378-TCDF and 1278-TCDF. The concentrations of these
compounds decrease drastically as the degree of substitution of chlorine with chlorine dioxide increases, and
cannot usually be detected at 60 % chlorine dioxide substitution or higher (typical detection levels for pulp
are approximately 0.1-1 pg/g, the corresponding levels for water samples 1-10 fg/g). The formation of
TCDD/F is strongly dependent on the ratio of molecular chlorine to lignin (3,5), usually defined as the
1805
1806

Kappa No. This ratio is also referred to as the molecular chlorine multiple. The main mechanism for the
formation has been found to be the chlorination of precursors, especially (unchlorinated) dibenzofuran (4,5).

The fact that no dioxins are detected when chlorine is replaced by chlorine dioxide is most probably because
chlorine dioxide does not have the same pronounced hydrogen/chlorine substitution ability as (molecular)
chlorine. In contrast to chlorine, chlorine dioxide mainly acts as an oxidation agent.

Large amounts of hexa, hepta and octa chlorinated dibenzo-p-dioxins, including predioxins, have also been
found in chlorophenolic formulations, used as wood preservative (6,7,8), and can contaminate, due to high
concentrations, e.g. effluents samples. The influence of such sources would easily be recognized from the
dioxin profile. Dioxin concentrations in pulp or pulp mill effluents are, however, often reported in terms of
Toxic Equivalence Factors, which may result in the bleaching process being erroneously considered to be
responsible for the dioxin emissions present in such effluents.

In addition, Berry et al (9) have investigated a variety of materials and shown that in some (including
unbleached pulp), the concentrations expressed as Toxicity Equivalence Factors, are often of magnitudes
higher than levels associated with pulp and paper.

As previously discussed there is scientific documentation that chlorine dioxide in modem bleaching
processes does not contribute to the formation of PCDD/F. The purpose of this investigation was to study
whether chlorine dioxide also has sufficient oxidizing power to destroy polyehlorinated dioxins and
dibenzofurans; at least to some extent. The concept was to expose a pulp, containing dioxins, to chlorine
dioxide, under similar conditions as those existing in a D-stage of a bleaching sequence, and monitor any
change in the dioxin content.

EXPERIMENTALS

Treatment with chlorine dioxide

The pulp used for the experiments was a non-oxygen delignified softwood kraft pulp of approximately
Kappa No 30 and bleached in a CEH sequence at the mill. The samples were taken from the H stage washer
and had a brightness of 72.4 % IS O, Kappa No. of 1.51, viscosity of 780 (dmVkg) and a dry solid content of
22 %. Two samples were taken to be used as duplicate reference samples in the determination of PCDD/F.

The treatment with chlorine dioxide was duplicated. Samples were treated in sealed polyethene bags with a
chlorine dioxide charge of 1.5 % on pulp, for 180 minutes at 70 ° C (158" F) at 10 % pulp consistency,
giving a final pH of 2.0-2.5. After the treatment the pulp was dewatered and the aqueous phase was then
filtered through the pulp mat (to retain as much of the fines as possible). The filtrates were collected for
determination of dioxins. The pulp samples were further washed with deionized water, and both this wash
water and the pulp were used for determination of dioxins.
 1807

The chlorine dioxide used in this experiment was produced from a modem SVP-lite process with non-
detectable levels of chlorine (< 10 rag/l), using the most sensitive analytical method available
(electrochemical detection).

Determination of polychlorinated dioxins and dibenzofurans.

The pulp samples, the aqueous filtrate samples and wash water samples were analysed using capillary gas
chromatography-mass spectrometry, according to the US Environmental Protection Agency method 1613A.
The determination included all tetra to oeta 2378 substituted congeners, the sum of all congeners of each
chlorination degree, as well as an additional 14 PCDF congeners (see Table 1 for details).

RESULTSAND DISCUSSIONS

There are potentially several ways of carrying out experiments for studying changes in dioxin concentrations
brought about by chlorine dioxide. One possible alternative is to spike a pulp sample with relatively high
concentrations of dioxins to facilitate the analytical determination. However, the risk that the dioxins may
inhomogeneously appear on the surface rather than penetrate the pulp cannot be overlooked.

Table 1. PCDD/PCDF Congeners included in the analyses

(US EPA = Environmental Protection Agency Method 1613,4)

1278-TCDF 1234678-HpCDF US EPA

2378-TCDF US EPA 1234679-HpCDF
2346-TCDF 1234689-HpCDF
2367-TCDF 1234789-HpCDF US EPA
Total TCDFs US EPA Total HpCDFs US EPA

12348-PeCDF OCDF US EPA

12367-PeCDF
12378-PeCDF US EPA
12468-PeCDF 2378-TCDD US EPA
12469-PeCDF Total TCDDs US EPA
23489-PeCDF
23478-PeCDF US EPA 12378-PeCDD US EPA
Total PeCDFs US EPA Total PeCDDs US EPA

123478-HxCDF US EPA 123478-HxCDD US EPA

123479-HxCDF 123678-HxCDD US EPA
123489-HxCDF 123789-HxCDD US EPA
123678-HxCDF US EPA Total HxCDDs US EPA
123789-HxCDF US EPA
124678-HxCDF 1234678-HpCDD US EPA
234678-HxCDF US EPA Total HpCDDs
Total HxCDFs US EPA
OCDD US EPA
 1808

While such an experiment could be very informative for identifying types of possible degradation
mechanisms, the analytical results would not be as representative, from a quantification point of view. In
spite of the analytical difficulties, the decision was taken to use a chlorine bleached sample from a pulp mill.

As previously stated, the formation of PCDD/F is mainly due to the chlorination of unchlorinated
precursors, especially dibenzofuran. It was therefore decided to include, along with all 2378 substituted
PCDD/F congeners, a further 14 PCDF congeners in order to monitor any potential chlorination as closely as
possible (Table 1).

For the first experiments, a pilot study was carried out, where two pulp samples were treated with chlorine
dioxide under identical conditions. These two samples, as well as two samples of the untreated CEH pulp,
were analyzed for PCDD/F.

The results of the experiments, summarized in Table 2, reveal that only four congeners could be
quantitatively analysed. The pattern can be considered as very typical for chlorine pulp bleaching, i.e. the
three predominant congeners were 2378-TCDD, 2378-TCDF and 1278-TCDF. The latter compound is not
included in the standard dioxin analytical procedures became it is not a 2378 substituted congener, but it
does serve as a "marker" for chlorine bleaching.

The overall reduction of dioxin concentrations after treatment with chlorine dioxide was 48 % (mean value
of all determinations). However, in this experiment no aqueous discharges were analyzed for PCDD/F.

Table 2.Concentrations of PCDD/F in pulp (pg/g) from the first experiment.

=D-bleached" indicates chlorine dioxide treated samples.

Untreated Untreated D-bleached D-bleached Mean value Mean value Percent

Sample 1 Sample 2 Sample 1 Sample 2 untreated D-bleached remaining]

2378-TCDD 2.0 2.1 1.0 1.0 2.1 1.0 48%

Sum TCDD 2.0 2.1 1.0 1.0 2.1 1.0 48%
2378-TCDF 3.2 3.3 1.5 1.7 3.3 1.6 49%
Sum TCDF 8.9 94 3.7 3.9 9.2 3.8 42%
Sum PeCDF 1.2 1.1 0.6 < 0.58 1.2 0.5 51%
1278-TCDF 2.1 2.1 1.8 11 2.1 1.5 69%
12468-PeCDF 1.2 1.1 0.6 < 0.29 1.2 0.4 39%

The aim of the second set of experiments was to attempt to establish a pseudo mass balance to calculate an
actual degradation of dioxins. The same conditions were applied as in the first experiments, but here the
water phases from the experiments were also analysed.
 1809

The results, summarized in Tables 3a + b and Fig. I, were seen to be consistent with those obtained in the
first pilot experiments. Additionally, the concentrations in the water samples were found to be low and did
not contribute substantially to the overall level.

Table 3a. Concentrations of PCDD/F in pulp and water sample (fg/g) from the second experiment
("D-bleached" indicates chlorine dioxide treated samples).

Untreated pulp Untreated pulp D-bleached pulp D-bleached pulp

Sample I Sample 2 Sample 1 Sample 2
2378-TCDD 2.4 2.7 1.4 1.7
2378-TCDF 3.4 3.5 1.9 2.0

1278-TCDF 2.5 2.7 1.5 1.7

12468-PeCDF 1.1 0.8 0.9 < 0.5

Sample amount (g) 300 g 300 g 300 g 300 g

Table 3b. Concentrations of PCDD/F in water samples (pg/l) from the second experiment.

Filtrate Filtrate Wash water Wash water

Sample 1 Sample 2 Sample 1 Sample 2
2378-TCDD < 6.8 < 7.5 < 6.1 < 6.1

2378-TCDF 5.5 5.2 4.7 5.0

1278oTCDF 5.3 5.1 3.8 4,0
12468-PeCDF < 3.8 < 3.1 < 2.9 < 2.9
Sample amount (I) 0.69 0.68 3.48 3.48

It should be pointed out that a true mass balance is very difficult. Even iftheoreticaUy all 75 congeners of
PCDD and 135 congeners of PCDF had been analysed, it would still not been possible to obtain a true mass
balance as a substantial part of the dioxins would most probably have been oxidized into unidentified water
soluble degradation products.

A potential pitfall in this kind of investigation is the precision of the analytical method. As can be seen from
the results in Tables 2 and 3 there was a high degree of analytical precision. The difference of PCDD/F
concentrations between the duplicate samples was less than 12 % of the mean value, which is more than
acceptable, especially at these relatively low levels.
1810

Fig.1. Levels of PCDD/F after treatment with chlorine dioxide

(mean values of duplicate samples)
100%

90%

80%

70%
"o
e
¢o 60%

50%
"6
40%

30%
(3.

20%

10%

0%
2378-TCDD 2378-TCDF 1278-TCDF 12468-PeCDF

There are several possible explanations to the decrease in dioxins observed. Theoretically, the changes can
either be explained as oxidation/degradation of the three TCDD/F congeners, and/or a further chlorination of
these compounds. The latter is not plausible as no substantial increase in the 2378 substituted penta-octa
congeners, nor in the 13 additional 2378 non-substituted PCDF, could be observed. On the contrary, the
quantity of the only congener, with a higher degree of chlorination than tetra, that could be detected, Le.
12468-PeCDF, consistently decreased as a result of the chlorine dioxide treatment.

Another explanation could be that dioxins, partially evaporated during the experiment. This possibility is
most unlikely. These compounds, though very apotar, have sufficient high molecular weights to remain
quantitatively on the pulp matrix.

The only plausible explanation is that there is actually a partial degradation of dioxins, as a result of the
chlorine dioxide treatment, though the mechanism has yet to be explored. However, the breakdown of the
aromatic nucleus in the lignin, during chlorine dioxide bleaching, is usually explained by the splitting of the
nucleus and the subsequent formation of dicarboxylic acid. A similar reaction could possibly be responsible
for the degradation of the aromatic dioxin molecules, in spite of the latter being more chemically stable due
to the deactivating ability of the chlorine atoms. An alternative could be that chlorine dioxide attacks the ether
link in the different congeners.

Furthermore, it has been observed that fully bleached kraft pulps, using modem bleaching techniques, contain
less dioxins than unbleached kraft pulps (9). This can be held in support of the argument that chlorine dioxide
actually has sufficient oxidation power to partially destroy dioxins.
 1811

In conclusion, the results obtained in this investigation clearly demonstrate the principal difference between
bleaching with chlorine and chlorine dioxide. Chlorine is well known for its ability to oxidize organic
compounds as well as to substitute hydrogen for chlorine atoms, resulting in polyehlorinated organic
compounds. On the contrary, as confirmed in previous studies, chlorine dioxide was not found to have any
contributory effects on the formation of PCDD/F, but the results previously discussed strongly indicate that
PCDD/F from sources other than bleaching can actually be degraded by chlorine dioxide treatment.

ACKNOWLEDGMENT

The authors wish to acknowledge their gratitude to Alta Analytical Laboratories, E1 Dorado Hills, CA (USA)
for skilfully carrying out the dioxin determinations.

LITERATURECITED

1. 0berg L G, W~gman N, Andersson R, Rapp¢ C. Organohalogen Compd. (13th International

Symposium on chlorinated Dioxins and related compounds, Vienna 1993) 297-302.

2. Asplund G (1992). On the Origin of Organohalogens found in the Environment. Thesis

Link6ping, Sweden 1992.

3. Axeg~d P, Renberg L .Chemosphere 19 (1988) 661-668.

4. Berry R M, Flemming B I, Voss R H, Luthe C E, Wrist P F Pulp & Paper Canada 90:8 (1989)
T279-289.

5. Rappe C, Swanson S, Glas B, Kringstad K, DeSouza F, Johansson L, Abe Z Pulp & Paper Canada
98:8 (1989) T273-278.

6. Jensen S, Renberg L. Ambio I (1972) 62-66.

7. Rappe C., Nilsson, C.A. J Chromatorgr. 67 (1972) 351.

8. LutheCE, BerryRM, VossRH, TappiJ. 76:3(1993)63-69.

9. Berry, R.M., Luthe,C.E., and Voss R.H., Environm. Sci. Technol. 27:6 (1993) 1164.