Environmental Toxicology and Chemistry, Vol. 21, No. 2, pp. 245–252, 2002
q 2002 SETAC
Printed in the USA
0730-7268/02 $9.00 1 .00
SOURCES AND DISTRIBUTION OF POLYCHLORINATED DIBENZO-p-DIOXINS AND
DIBENZOFURANS IN SEDIMENTS FROM MASAN BAY, KOREA
SOOK HYEON IM,† KURUNTHACHALAM KANNAN,*† MUNEAKI MATSUDA,‡ JOHN P. GIESY,† and
TADAAKI WAKIMOTO‡
†National Food Safety and Toxicology Center, Department of Zoology, Institute of Environmental Toxicology, Michigan State University,
East Lansing, Michigan 48824, USA
‡Department of Environment Conservation, Ehime National University, Tarumi 3-5-7, Matsuyama 790-8566, Japan
( Received 28 March 2001; Accepted 19 July 2001)
Abstract—Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDDs/DFs) were measured in sediments collected from Masan
Bay, Korea. Almost all tetra- through octachlorinated PCDDs/DFs were identified, including the 17 2,3,7,8-substituted PCDDs/
DFs. Total concentrations of PCDDs/DFs in sediments ranged from 102 to 6,493 pg/g dry weight. Concentrations of 2,3,7,8tetrachlorinated dibenzo-p-dioxin (TeCDD) equivalents (TEQs) in sediments estimated based on I-TEFs were in the range of 1 to
76 pg/g dry weight. Total concentrations of PCDDs/DFs in Masan Bay sediments were comparable to those reported for the Rhine
and Humber Rivers on the North Sea, the Housatonic River in the United States, and some rivers and lakes in Japan and the United
Kingdom. A spatial gradient of total concentrations of PCDDs/DFs decreased toward the open sea. Two of the 11 sampling sites
near the coastal zone contained relatively great concentrations, suggesting the presence of point sources. The homologue composition
of PCDFs in sediments from two highly contaminated locations in Masan Bay was correlated with that of commercial polychlorinated
biphenyl (PCB) preparations, such as Kanechlors 300, 400, or 500. The wide range of PCDD isomers and greater concentrations
of PCDDs than of PCDFs at certain locations suggest that, in addition to technical PCB preparations such as Kanechlors, other
sources, like solid waste incineration, uncontrolled trash burning, and pentachlorophenol, have contributed to the contamination.
Keywords—Polychlorinated dibenzo-p-dioxins
Dibenzofurans
Sediments
Toxic equivalents
Masan Bay
Korea
are a reservoir for hydrophobic contaminants like PCDDs/DFs
[12–15], assessment of contaminants in sediments of estuaries
has been a major research topic for several years. While research has focused on assessing exposure to and toxicity of
PCDDs/DFs, little attention has been given to identification of
sources in Asian countries like Korea. The objectives of this
research were to measure concentrations of PCDDs/DFs in
sediments of Masan Bay, to identify sources, and to determine
the primary factors affecting concentrations of PCDDs/DFs in
sediments.
INTRODUCTION
In Korea, a wide variety of pesticides and chemicals have
been used in agricultural and industrial production. Among
various chemical contaminants, the issue related to emissions
of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) and exposure of humans has
evoked great public concern. The PCDDs/DFs can be emitted
from a number of activities, including industrial processes,
municipal and industrial waste incineration, automobile exhaust, and natural events such as forest fires [1–5]. However,
monitoring surveys on the extent of PCDDs/DFs contamination in Korea are limited. Thus, a need exists for monitoring
environmental distribution and sources of PCDDs/DFs in the
Korean environment.
Masan Bay is located in southeastern Korea and is a semiclosed estuary with an average depth of 10 to 20 m and a
surface area of 16 km2. Approximately 780,000 people reside
around the bay, and several industrial complexes, including
petrochemical, metal processing, electrical, and plastics manufacturing, are located in this region. Masan Bay was selected
as a study area because the cities of Masan and Changwon
are moderately urbanized and industrialized areas and because
the bay and two cities represent diverse environments from
which samples of sediments, soils, fish, shellfish, and air could
be collected.
Because of their potential to cause carcinogenic and reproductive effects, PCDDs/DFs have been given priority for study
in Korea as well as other countries [6–11]. Because sediments
MATERIALS AND METHODS
Masan Bay was divided into three regions for sampling,
encompassing the near coastal area, the continental shelf, and
the near open sea (Fig. 1). Sediments were collected from 11
locations in June 1992 using a stainless-steel Eckman dredge.
Samples were placed in polyethylene bags and stored at 48C
until analysis. Analytical methods for PCDDs/DFs in sediments have been reported in detail elsewhere [12]. Briefly,
sediment samples were air dried in a cool dark place and twigs
and pebbles removed. Sediment samples were ground with a
mortar and pestle, then sieved through 0.34-mm mesh. Sediments were Soxhlet extracted with 500 ml isopropanol for 24
h followed by 500 ml dichloromethane for 24 h. Known
amounts of 13C-labeled PCDDs/DFs were added as internal
standards. After Kuderna–Danish concentration, the solvent
was transferred to hexane and treated with concentrated sulfuric acid. Before a series of silica gel, alumina, and activated
carbon column cleanup, activated copper was used to remove
elemental sulfur. A high-resolution gas chromatograph, interfaced with a high-resolution mass spectrometer, was used for
* To whom correspondence may be addressed
(kuruntha@msu.edu).
245
246
Environ. Toxicol. Chem. 21, 2002
Fig. 1. Locations from which sediment samples were collected from
Masan Bay, Korea.
the identification and quantification of PCDDs/DFs. A Hewlett-Packard 5890 series II gas chromatograph (Avondale, PA,
USA), connected to a JEOL SX102A high-resolution mass
spectrometer, was employed. The capillary column was 50 m
long, with a 0.25-mm i.d. and 0.2-mm stationary phase film
thickness (CP-Sil 88, Chromopack, Supelco, Bellefonte, PA,
USA). The temperature program was held at 708C for 1 min
and then increased at a rate of 208C/min to 1808C, held for 1
min, and then increased at a rate of 28C/min to 2408C. The
mass spectrometer was operated under electron impact mode
at 70 eV. The PCDD/DF isomers and congeners were determined by selected ion monitoring at the two most intensive
ions of the molecular ion cluster. Recoveries of 13C-labeled
internal standards ranged from 78 to 86%. Reported concentrations were corrected for the recoveries of internal standard.
Identification and quantification of PCDDs/DFs were performed by means of internal and external standards. A fly ash
sample containing known compositions of PCDD/DF congeners was used as a reference to identify individual PCDDs/
DFs. Procedural blanks were analyzed for every five samples
to check for interferences and laboratory contamination. Concentrations of PCDDs/DFs are reported as the sum of all the
quantifiable isomers and congeners. Concentrations that were
less than the method detection limits were assigned zero when
calculating means.
RESULTS AND DISCUSSION
Almost all tetra- through octachlorinated PCDDs/DFs were
present in all sediment samples (Table 1). Total concentrations
of PCDDs/DFs and 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents in sediments ranged from 102 to 6,493 pg/g dry weight
and from 1 to 76 pg/g dry weight, respectively. Although the
concentrations varied considerably among the 11 sampling locations, a positive relationship was observed between concentrations of total PCDDs/DFs and concentrations of TEQs.
S.H. Im et al.
Measured total concentrations of PCDDs/DFs in Masan Bay
sediments (102–6,493 pg/g dry wt) were comparable to or
slightly less than those found in other industrialized countries.
The greatest concentrations observed in sediments of the Rhine
and Humber Rivers along the estuarine and coastal North Sea
ranged between 1,846 and 10,557 pg/g dry weight [16]. Concentrations of PCDDs/DFs in sediments of the Housatonic
River in the United States ranged from 160 to 5,400 pg/g dry
weight, except in one sample that contained a concentration
of 82,000 pg/g dry weight [17]. Total concentrations of
PCDDs/DFs in sediments from the United Kingdom rivers
ranged from 446 to 9,310 pg/g dry weight [18] and in Japan
ranged from 377 to 15,792 pg/g dry weight [19].
Total concentrations of PCDDs/DFs in sediments and the
spatial gradient were used to determine potential point sources
in Masan Bay (Fig. 2). Concentrations of PCDDs/DFs were
widely distributed even to site 11, which is near the open sea
and a productive fishing area. Maximum concentrations were
observed in sediments from the most industrialized sampling
locations, such as sites 1 and 6, then decreased along a spatial
gradient away from the coast and out to the continental shelf.
These results indicate that the point sources are in the vicinity
of sites 1 and 6 and reflect the importance of urban discharges
as sources of PCDDs/DFs to sediments. Previously, concentrations of PCBs at or near sites 1 and 6 have been reported
to be greater than the other areas of Masan Bay [13,20]. These
areas are urbanized and industrialized with chemical manufacturing, electrical processes, and steel production, all of
which could have contributed for PCDDs/DFs. In addition,
less flushing due to geographical characteristics, such as a long,
narrow inlet, results in localized sedimentation of PCDDs/DFs
in Masan Bay.
Different sources of PCDDs/DFs are characterized by different congener and homologue patterns [21,22]. These differences in patterns can be used to discern possible sources.
Although sediments at sites 1 and 6 were high in concentrations
of PCDDs/DFs, the patterns of relative concentrations were
different (Table 1 and Fig. 3). The total concentration of PCDFs
was sevenfold greater than that of PCDDs at site 1, while the
concentration of PCDFs was only 0.65 times the total concentration of PCDDs at site 6. The homologue composition of
PCDFs was similar between these two locations. Tetrachlorinated dibenzofurans (TeCDFs) contributed the greatest proportions, accounting for 58 and 42% of the total PCDFs concentrations at sites 1 and 6, respectively. The relative proportion of TeCDF was followed in decreasing order by penta
(PeCDF) . hexa (HeCDF) . hepta (HpCDF) . octachlorinated dibenzofuran (OCDF). In general, 70 to ;80% of the
total PCDF concentrations were attributable to lesser-chlorinated dibenzofurans, such as TeCDF and PeCDF homologues.
The PCDFs occur as trace contaminants in technical PCB
mixtures, and therefore the release of PCBs can be a significant
source of PCDFs in the environment [23–25]. The PCDFs
present in technical PCB mixtures have specific homologue
patterns that are distinct from those produced during combustion. Nearly all PCDF isomers and homologues have been
identified in Japanese PCB preparations such as Kanechlors
300, 400, 500, and 600 [25]. These PCB preparations did not
contain detectable amounts of PCDDs. The TeCDF homologue
represented 58 and 72% of the total PCDFs found in Kanechlors 300 and 400, followed in decreasing order by PeCDF,
HeCDF, HpCDF, and OCDF. Both TeCDF and PeCDF homologues contributed between 80 and 93% of the total PCDFs
TeCDDa
1368
1379
1378
1247 1 1248 1 1369
1268
1478
2378
1237
1234 1 1246 1 1249 1 1238
1279 1 1236
1278
1469
1239
1269
1267
1289
Total
PeCDDb
12479 1 12468
12368
12478
12379
12469 1 12347
12378
12369
12467
12489
12346
12367
12389
Total
HeCDDc
124679 1 124689 1 123468
123679 1 123689
123478
123678
123469
123789
123467
Total
HpCDDd
1234679
1234678
Total
OCDDe
12346789
Total PCDDs
4
3
0.3
2
0.4
0.1
,0.1
,0.1
,0.1
,0.1
0.1
,0.1
9.9
5
1
,0.1
0.5
,0.1
0.4
,0.1
6.9
2
,0.1
0.1
,0.1
,0.1
,0.1
,0.1
,0.1
,0.1
,0.1
,0.1
,0.1
2.1
7
3
,0.1
0.4
,0.1
0.3
,0.1
10.7
4
3
7
8
59.1
72
31
13
15
23
7
8
13
10
,0.1
20
6
218
57
37
7
9
5
10
2
127
33
26
59
207
820
1
66.7
2
1
3
19
7
0.9
1
0.4
,0.1
,0.1
6.5
10.5
0.6
,0.1
,0.1
,0.1
,0.1
,0.1
,0.1
45.9
3
22
8
0.3
1
,0.1
,0.1
,0.1
,0.1
,0.1
,0.1
,0.1
,0.1
,0.1
,0.1
,0.1
,0.1
31.3
2
34
16
13
35
12
6
5
14
24
19
4.5
4.5
5
9
5
3
209
1
7
87.3
6
7
13
9.6
3
1
2
0.1
1
0.3
17
5
5
0.5
3
1
0.8
0.3
0.5
0.3
,0.1
0.3
0.3
17
18
8
0.4
2
0.6
,0.1
0.3
1
2
1
,0.1
,0.1
,0.1
,0.1
,0.1
,0.1
33.3
4
5
144.2
8
8
16
19
6
1
2
0.5
1
1
30.5
10
7
1
5
2
1
0.5
1
0.1
,0.1
0.5
0.5
28.6
44
7
2
3
1
0.3
0.3
1.5
2.5
1
0.4
0.1
0.7
0.3
,0.1
,0.1
64.1
5
547
1,190
115
73
188
78
38
4
7
5
3
8
143
40
32
4
,0.1
11
4
4
2
2
,0.1
5
5
109
110
48
6
10
3
,0.1
1
3
6
5
2
1
3
2
3
,0.1
203
6
Sampling location
96
383
24
27
51
35
16
1
4
1
,0.1
5
62
22
14
1
10
4
2
1
,0.1
,0.1
,0.1
3
3
60
54
30
4
8
4
,0.1
,0.1
4
6
4
,0.1
,0.1
,0.1
,0.1
,0.1
,0.1
114
7
134
179.8
4
4
8
6
2
0.3
0.6
,0.1
0.4
0.3
9.6
4
3
0.3
2
0.6
0.4
0.1
0.2
0.2
,0.1
0.3
0.2
11.3
8
4
0.6
1
0.5
,0.1
,0.1
0.5
1.3
0.7
,0.1
0.3
,0.1
,0.1
,0.1
,0.1
16.9
8
81
205.5
29
20
49
16
7
1
2
0.5
1
0.3
27.8
8
4
0.7
3
2
0.5
,0.1
0.9
,0.1
,0.1
0.7
0.3
20.1
13
7
1
2
0.6
,0.1
,0.1
1
1.4
0.7
,0.1
0.6
,0.1
0.3
,0.1
,0.1
27.6
9
Table 1. Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDDs/DFs) concentrations (pg/g, dry wt) of sediments from Masan Bay, Korea
23
135.8
20
15
35
20
6
,0.1
2
,0.1
2
0.7
30.7
7
6
0.7
4
1
0.5
0.3
0.4
0.4
,0.1
0.5
0.3
21.1
15
7
,0.1
3
,0.1
,0.1
,0.1
0.1
0.1
0.8
,0.1
,0.1
,0.1
,0.1
,0.1
,0.1
26
10
46
93.9
6
4
10
7
3
0.3
0.7
,0.1
0.5
,0.1
11.5
4
3
0.2
2
0.6
0.3
,0.1
0.2
0.1
,0.1
0.2
0.2
10.8
9
4
0.5
0.9
0.3
,0.1
,0.1
0.1
0.1
0.5
,0.1
0.2
,0.1
,0.1
,0.1
,0.1
15.6
11
Dioxins in Korean sediments
Environ. Toxicol. Chem. 21, 2002
247
TeCDFf
1368
1378 1 1379
1347
1468
1247 1 1367
1348
1346
1248
1246 1 1268
1237 1 13691 1478
1234 1 1678
1238 1 1467 1 1236
2468
1349
1278
1267 1 1279
1469
1249
2368
2467
1239
2347
1269
2378
2348
2346
2367
3467
1289
Total
PeCDFg
13468
12468
13678
13479
13478 1 12368
12478
12479 1 13467
12467
12347
14678
13469
12348 1 12378
12346
12379
12367
12469 1 12678
12679
12369
23468
0.7
0.7
0.3
0.4
0.9
0.4
0.3
0.3
0.5
1.5
0.4
1
2
0.1
0.6
0.4
0.2
0.4
0.2
0.4
0.2
0.1
0.1
0.4
0.3
0.3
0.4
0.3
,0.1
13.8
0.5
0.8
0.5
0.5
0.7
0.6
0.5
0.3
0.3
0.3
0.2
0.6
0.2
0.2
0.3
0.5
0.2
0.2
0.2
77
82
46
55
70
65
106
99
63
63
19
69
40
40
48
79
30
7
40
2
102
84
102
127
212
91
118
118
180
258
203
300
60
23
91
135
110
21
10
181
70
53
10
37
116
175
155
115
12
3,269
1
0.8
1
0.6
1
1.2
2
0.8
0.8
0.5
0.5
0.2
2
0.3
0.3
0.5
0.9
0.3
,0.1
0.9
0.9
1
0.6
0.7
1
0.4
0.5
0.5
0.6
0.8
1
1
2
1
1.9
0.6
0.4
0.6
0.3
0.6
0.5
0.4
0.5
0.7
1
0.5
0.1
,0.1
,0.1
20.1
4
3
3
2
2.5
3.5
3
3
3
2
2
0.3
4
1.5
1.5
2
3
0.4
0.5
3
3
4
2
2
5
2
2
2
0.4
4
3
4
3
0.4
3
3
1
2
1
4
2
5.4
0.3
0.7
3
2
3
2
0.2
69.4
5
9
10
6
11
14
17
13
18
6
11
8
2
5
5
8
5
6
1
13
10
17
10
10
22
8
8.5
8.5
12
30
11
20
18
3
18
25
20
3
15
11
5
4
3
6
8
5
10
4
5
330
6
4
6
2
5
4
9
2
4
1.5
1.5
0.7
2
0.5
0.5
2
4
2
,0.1
4
,0.1
4
,0.1
,0.1
4
2
2
2
2
2
,0.1
5
6
,0.1
6
3
1
2
1
3
5
2
,0.1
3
5
2
3
,0.1
,0.1
65
7
0.4
0.6
0.3
0.5
0.6
1
0.4
0.5
0.3
0.3
0.1
0.6
0.2
0.2
0.3
0.5
0.2
0.1
0.3
0.4
0.7
0.4
0.4
0.7
0.3
0.4
0.3
1
1
0.4
1
1
,0.1
0.8
0.5
0.2
0.3
0.1
0.6
0.1
0.2
,0.1
6
3
0.3
0.7
0.4
,0.1
21.2
8
2
4
1
1.5
1.8
3
2
2
1
1
0.5
3
0.5
0.5
1
1.3
1
0.3
1
1
2
0.9
0.9
2
0.7
1
1
1
0.5
2
2
2
0.1
2
2
0.5
0.5
0.3
2
0.5
0.1
0.1
1.9
0.7
1.5
2
0.7
,0.1
31.9
9
1
2
0.8
1
1.2
2
1
1
1
1
0.2
2
0.5
0.5
0.8
,0.1
0.1
0.9
1
0.6
0.9
0.4
0.4
1
0.4
0.5
0.5
1
1
0.9
1
1
0.1
1
0.7
0.2
0.4
0.2
0.9
0.2
1
,0.1
0.7
0.4
0.4
0.9
0.4
,0.1
17.1
10
0.4
0.9
0.3
0.5
0.1
1
0.4
0.4
0.3
0.3
0.1
1
0.1
0.1
0.2
0.3
0.7
0.1
0.3
0.4
0.6
0.3
0.3
0.6
0.2
0.3
0.2
0.5
0.3
0.3
0.3
0.7
0.1
0.3
0.4
0.3
0.1
0.1
0.4
0.1
0.2
0.3
0.4
0.1
0.2
0.3
0.2
,0.1
8.5
11
Environ. Toxicol. Chem. 21, 2002
0.6
11
0.5
0.5
0.7
1
0.6
0.6
0.3
0.3
0.2
1
0.3
0.3
,0.1
0.3
1.2
0.2
0.3
1
0.9
0.4
0.6
1
0.4
0.5
0.4
0.5
1.5
0.7
1
2
0.9
,0.1
0.6
0.3
0.4
0.2
1
0.2
0.2
,0.1
0.4
0.4
0.4
0.5
0.4
,0.1
16.8
3
Sampling location
Table 1. Continued
248
S.H. Im et al.
0.9
0.6
2
,0.1
0.6
0.6
,0.1
1
,0.1
0.3
0.3
,0.1
0.3
6.6
7
,0.1
7
,0.1
14
,0.1
59
43
102
0.7
1
85
132
122
16
62
59
6
123
5
16
10
5
66
707
300
56
16
,0.1
372
,0.1
820
5,673
6,493
6.9
76
b
a
,0.1
67
56
123
0.8
1
2
,0.1
,0.1
,0.1
2
2
3
4
0.5
2
2
0.5
1
,0.1
0.3
,0.1
,0.1
0.9
16.2
0.2
,0.1
0.5
,0.1
0.6
21.2
,0.1
0.2
0.3
,0.1
0.2
8.3
7
5
70
2
143
1,325
TeCDD 5 tetrachlorodibenzo-p-dioxin.
PeCDD 5 pentachlorodibenzo-p-dioxin.
c HeCDD 5 hexachlorodibenzo-p-dioxin.
d HpCDD 5 heptachlorodibenzo-p-dioxin.
e OCDD 5 octachlorodibenzo-p-dioxin.
f TeCDF 5 tetrachlorodibenzofuran.
g PeCDF 5 pentachlorodibenzofuran.
h HeCDF 5 hexachlorodibenzofuran.
i HpCDF 5 heptachlorodibenzofuran.
j OCDF 5 octachlorodibenzofuran.
k TEQs 5 toxic equivalency quotients.
12349
12489
23478
12389
23467
Total
HeCDFh
123468
1346878 1 134679
124678
124679
123478 1 123479
123678
124689
123467
123679
123469 1 123689
123789
123489
234678
Total
HpCDFi
1234678
1345679
1234689
1234789
Total
OCDFj
12346789
Total PCDDs
Total PCDFs
Total PCDDs 1 PCDFs
Quotient PCDFs/PCDDs
TEQsk
3
2
1
,0.1
87
85
172
1
4
9
0.3
0.9
0.3
10.5
3
4
7
0.8
9
6
0.8
3
0.5
0.6
0.6
0.5
2
37.8
0.2
0.2
0.9
,0.1
0.5
16.4
4
,0.1
144
211
355
1.5
5
19
5
3
,0.1
27
9
11
11
1
10
11
1
2
0.8
1
1
0.6
5
64.4
0.3
0.3
2
0.2
3.7
49.7
5
12
1,190
782
1,972
0.7
21
48
2
1
1
52
23
27
31
4
14
10
,0.1
37
12
4
6
2
13
183
2
2
20
,0.1
13
205
6
Sampling location
Table 1. Continued
30
383
284
667
0.7
9
36
12
,0.1
,0.1
48
6
9
15
1
19
11
,0.1
7
,0.1
1
5
,0.1
4
78
,0.1
,0.1
4
,0.1
4
62.7
7
,0.1
180
45
225
0.3
2
3
0.2
0.5
,0.1
3.7
0.9
1
2
0.2
3
2
0.4
0.8
,0.1
0.2
,0.1
,0.1
0.7
11.2
,0.1
,0.1
0.7
,0.1
0.5
8.6
8
,0.1
206
152
358
0.7
3
42
,0.1
17
,0.1
59
4
3
8
0.5
4
2
2
2
,0.1
0.5
2
0.2
1
29.2
0.2
,0.1
0.9
,0.1
2
31.5
9
,0.1
136
97
233
0.7
2
33
2
7
,0.1
42
2
3
4
0.3
3
2
0.5
1
,0.1
0.5
,0.1
0.2
0.6
17.1
,0.1
0.2
0.9
0.5
1
20.6
10
,0.1
95
51
146
0.5
1
13
,0.1
5
,0.1
18
0.8
9
2
0.2
2
1
0.4
0.5
,0.1
0.2
0.2
0.2
,0.1
16.5
0.1
0.1
0.2
,0.1
0.4
8.3
11
Dioxins in Korean sediments
Environ. Toxicol. Chem. 21, 2002
249
250
Environ. Toxicol. Chem. 21, 2002
S.H. Im et al.
Fig. 2. Total concentrations of polychlorinated dibenzo-p-dioxins and
dibenzofurans (PCDDs/DFs) (pg/g dry wt) at each sampling location
in sediments collected from Masan Bay, Korea.
in Kanechlors 300 and 400. Greater proportions of TeCDF and
PeCDF homologues in sediments at sites 1 and 6 correspond
well with those reported for Kanechlors 300 and 400. Furthermore, significant linear correlations existed between PCDF
homologue compositions in sediments at sites 1 and 6 and the
Kanechlor preparations (Figs. 4 to 6).
The composition of PCDFs in sediments from site 1 was
as follows: TeCDF (57.6%), PeCDF (23.4%), HeCDF (12.5%),
HpCDF (6.6%), and OCDF (0%). For Kanechlor 300, the homologue composition of PCDFs is as follows: TeCDF (58.2%),
PeCDF (21.4%), HeCDF (14.2%), HpCDF (4%), and OCDF
(2.3%). A significant correlation was observed between sediment and Kanechlor 300 profiles of PCDFs (Fig. 4; r 5 0.99).
Similar to that for Kanechlor 300, a significant correlation (r
5 0.99) existed between the PCDFs homologue distribution
at site 1 sediments and Kanechlor 400 (Fig. 5). The proportion
of PCDF homologues in Kanechlor 400 is TeCDF (72.3%),
PeCDF (20.9%), HeCDF (5.1%), HpCDF (1.05%), and OCDF
(0.77%), respectively. No significant correlation was observed
between profiles of PCDFs in sediments from site 1 and those
in Kanechlors 500 or 600. Similarly, when relative concentrations of individual isomers from each homologue group of
PCDFs in sediments were compared with those in Kanechlors,
Fig. 3. Concentrations (pg/g dry wt) of polychlorinated dibenzo-pdioxins and dibenzofurans (PCDDs/DFs) homologues at each sampling location. Both site 1 and site 6 are near probable point sources
of PCDDs/DFs contamination. Distinctive inputs of PCDFs relative
to PCDDs were observed at site 1.
Fig. 4. Correlation of relative proportion of polychlorinated dibenzofurans (PCDFs) homologues at site 1 of this study (x-axis) with
Kanechlor (KC) 300 preparation given by Wakimoto et al. [25] (yaxis). Each homologue is expressed as the percentage of total PCDFs.
few isomers were less in sediments than that in Kanechlors
300 and 400. This could be due to selective degradation of
certain PCDF congeners in sediments. Despite this, the results
suggest that technical PCB mixtures may be one of the possible
sources of PCDFs in sediments at site 1. Concentrations of
PCBs in sediment near sites 1 and 6 were in the range of 150
to 200 ng/g dry weight [12,13,20]. Although concentrations
of PCDDs were greater than those of PCDFs at site 6, the
PCDFs homologue pattern in sediments from site 6 was correlated with those in Kanechlor 300 (r 5 0.93) (Fig. 6), 400
(r 5 0.87), and 500 (r 5 0.66). The greater concentrations of
PCDFs than of PCDDs and the correlation of the PCDF homologue pattern in sediments with technical PCBs suggest
sources originating from technical PCB preparations. Furthermore, the presence of a series of PCDD isomers at both
Fig. 5. Correlation of relative proportion of polychlorinated dibenzofurans (PCDFs) homologues at site 1 of this study (x-axis) with
Kanechlor (KC) 400 preparation given by Wakimoto et al. [25] (yaxis). Each homologue is expressed as the percentage of total PCDFs.
Environ. Toxicol. Chem. 21, 2002
Dioxins in Korean sediments
5.
6.
7.
8.
9.
Fig. 6. Correlation of relative proportion of polychlorinated dibenzofurans (PCDFs) homologues at site 6 of this study (x-axis) with
Kanechlor (KC) 300 preparation given by Wakimoto et al. [25] (yaxis). Each homologue is expressed as the percentage of total PCDFs.
10.
11.
site 1 and site 6 suggest the occurrence of other sources as
well.
Among possible sources of PCDDs, thermal processes, such
as municipal and chemical waste incineration (including uncontrolled trash burning), hospital waste incineration, and other combustion processes, can result in the production of a range
of PCDD isomers [26–28]. Pentachlorophenol production also
results in significant releases of OCDD [29]. A wide range of
tetra- through octachlorinated PCDD isomers were identified
in all samples from Masan Bay, and great concentrations of
OCDD at certain locations, including site 6, were present. This
suggests sources originating from incineration and possibly
from the use of pentachlorophenol. Only 4% of the municipal
and industrial waste are incinerated in Korea, while in other
industrialized countries up to 74% of the waste is treated [30].
No incinerators exist nearby Masan Bay, but uncontrolled open
burning of industrial wastes has been identified in the vicinity
of this bay. These incineration activities are currently a major
source of PCDDs.
In summary, concentrations of PCDDs/DFs in sediments
from Masan Bay are comparable to those in sediments in other
industrialized countries. At least two point sources of PCDDs/
DFs have been identified in the industrial zone of Masan Bay.
The PCDDs/DFs homologue profile in certain highly contaminated locations suggested a source originating from commercial PCB preparations. In addition, uncontrolled incineration of industrial wastes in open areas and the usage of pentachlorophenol have contributed for the PCDDs/DFs sources
in Masan Bay.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
1.
2.
3.
4.
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