Endocrine Disrupting Compounds in Korea
2001
Jae Ryoung OH, Donghao Li and Won Joon Shim
Chemical
Oceanography Div.
Korea Ocean
Research & Development Institute
Ansan P.O.Box
29
e-mail: jroh@kordi.re.kr
1. Introduction
Alkylphenol ethoxylates(APEs), chlorophenols(CPs) and
bisphenol-A(BPA) have been widely used in the preparation of detergents, wood
preservatives and polymeric materials for household and industrial
applications. They have been discharged
directly or indirectly to environment, and contaminated the atmosphere, water
and soil. APEs are degraded to
alkylphenols(APs) during aerobic or anaerobic waste treatment process or by
micro-organism and photolysis in the nature.
Although the APEs are less toxic to organism, their metabolites show
high toxicity to organisms. So most
countries including
Phthalates
have a broad range of applications. Phthalate
esters are liquid plasticizers, similar in appearance to vegetable oils, which
are added to a hard plastic called polyvinyl chloride (PVC or vinyl). The liquid phthalates act as a softener
causing the PVC, which is hard in its raw form, to become flexible. Phthalates
have made possible a wide range of flexible vinyl products which have improved
the quality of life in homes, offices and hospitals for more than several tens
years, including vinyl wall covering flooring, upholstery, wire and cable
sheathing, medical products, packaging and toys. Unplasticized PVC is hard – it
might be used in such applications as piping or plumbing fixtures. Phthalates may also be used to lubricate
and/or enhance the durability and longevity of other materials. Such applications include detergents, solvents,
lubricating oils and personal care products, such as lotions, nail polish,
perfumes and pharmaceuticals(http://www.phthalates.org/html/pegenhow.htm). Phthalates exhibit very low direct acute
toxicity. However, long time exposure has shown toxic effects on testes, kidney
and liver in animal experiments.
Table
1 shows the target analytes of phenolic compounds, phthalates and
organochlorine pesticides.
Table 1. Target compounds in coastal seawater
|
Phenols(11) |
Phthalates(9) |
Pesticides(10) |
|
t-butylphenol(t-BP) |
diethylphthalate(DEP) |
a-HCH |
|
n-butylphenol(t-BP) |
dipropylphthalate(DprP) |
b-HCH |
|
n-pentylphenol(n-PP) |
dibutylphthalate(DBP) |
g-HCH |
|
n-hexylphenol(n-HexP) |
dipentylphthalate(DPP) |
d-HCH |
|
n-heptylphenol(n-HepP) |
butylbenaylphthalate(BBP) |
p,p’-DDD |
|
t-octylphenol(t-OP) |
dihexylphthalate(DHexP) |
p,p’-DDE |
|
n-octylphenol(n-OP) |
dicycrohexylphthalate(DCHP) |
p,p’-DDT |
|
nonylphenol(NP) |
diethylhexyladipate(DEHA) |
aldrin |
|
2,4-dichlorophenol(DCP) |
diethylhexylphthalate(DEHP) |
dieldrin |
|
pentachlorophenol(PCP) |
|
endrin |
|
bisphenol-A |
|
|
2. Sampling Procedures
Water
samples were collected by using pre-cleaned one liter amber glass bottles with
teflon-lined caps. Duplicate samples
were collected from each sampling sites.
The sampling personnel wore latex gloves during sampling. The personnel put the bottle under the
surface of the water as it is closed and open it till it becomes a half
full. Close the bottle and take it
out. Shake the bottle 10 seconds and
discard water from the bottle. Put the
bottle under the surface of the water as it is closed again and open it till it
becomes full. Close the bottle and take
it out. Open the cap and add surrogate
standards to the sample. Store the
sample in the room temperature and ship back to the laboratory as soon as
possible. If it is not possible to
analyze the sample immediately, extract the sample with solvent.
2. 1. Selection of Location
Coastal
water sampling sites were selected according to the following criteria:
· The site shall be outside
the zone of initial dilution of a dumpsite or point-source discharge, and easy
to access
· The sampling sites will coincide with historical monitoring sites (i.e., on-going Korea Ministry of Environment Endocrine Disruptors Monitoring Program) when feasible and all other criteria are met.
Sampling
sites of coastal seawater is shown in Fig. 1.
2. 2. Conditions During Sample Collection
The
weather was fine during water sampling in September, 2001 and January,
2002. Most sampling dates in September
were sunny and air temperature was quite hot.
Sampling dates in January were sunny and no snowing during sampling
period.
3. Analytical Results
All
the samples were analyzed by using Shimadzu GC-MS QP5000.
3. 1. Summary of Results
Organochlorine pesticides in
water
Not
like 1999 and 2000, all the surficial waters were below detection of organochlorine
pesticides in summer and winter.
Phenolic compounds in seawater
Summer
The
total phenolic compounds concentrations ranged from 60 to 285 ng/L (Table
3). In our samples, the most abundant
phenolic compounds were Nonylphenol and Bisphenol-A. Nonylphenol was detected
in all samples. 4-t-Butylphenol was
present in 8 samples out of 9.
t-Ocytlphenol was present in 7 samples out of 9. 4-n-Butylphenol, n-Pentylphenol,
4-n-Hexylphenol, n-Heptylphenol and n-Octylphenol were not detected at
all. The total alkylphenol
concentrations ranged from 46 (Uljin) to 182 ng/L (
Chlorophenols
were not detected at all.
Bisphenol
A was detected in all samples. The
concentrations ranged from 14 (Uljin) to 137 ng/L (
Winter
The
total phenolic compounds concentrations ranged from 31 to 1736 ng/L (Table
4). The most abundant phenolic compound
was nonylphenol like summer.
4-t-Butylphenol t-Octylphenol were present in 8 samples out of 9. Nonylphenol and Bisphenol A were detected in
all samples. 4-n-Butylphenol,
n-Pentylphenol, 4-n-Hexylphenol, n-Heptylphenol and n-Octylphenol were not
detected at all. The total alkylphenol
concentrations ranged from 18 (Uljin) to 1392 ng/L (Busan). Busan showed extremely high level of
Nonylphenol. The alkylphenols
concentrations were generally lower than summer except Busan and
Chlorophenols
were not detected at all.
Bisphenol
A was detected in all samples. The concentrations
ranged from 12 (Shiwha) to 344 ng/L (Busan).
Busan and
Phthalates in seawater
Summer
The
total phthalates concentrations ranged from undetected to 246 ng/L (Table
6). In our samples, the most abundant
phthalates compounds were DBP and DEHP.
DBP was present in 5 samples out of 8 and DEHP was present in 7 samples
out of 8. DEP, DprP, DPP, BBP, DhexP, DCHP and DEHA were not detected at all. DBP concentrations ranged from undetected to
59 ng/L. DEHP concentrations ranged from
undetected to 311 ng/L. The level of
DEHP was generally much higher than DBP.
Winter
The
total phthalates concentrations ranged from 17 to 304 ng/L (Table 7). Like summer, the most abundant phthalate
compounds were DBP and DEHP. DBP was
present in 5 samples out of 9 and DEHP was present in 9 samples out of 9. DEP, DprP, DPP, BBP, DhexP, DCHP and DEHA
were not detected at all. DBP
concentrations ranged from undetected to 122 ng/L. DEHP concentrations ranged from 17 to 182
ng/L. Like summer, all sites showed
higher level of DEHP than DBP except
3. 2. Summary of Quality Assurance/Control Measures
Calibration
A
five-point calibration curve established the response of the detector. The calibration curve was prepared using a
linear calibration equation. The
calibration solutions were analyzed in the beginning and at the end of the
analytical GC-MS run.
Method blank analysis
An
acceptable method blank analysis did not contain any target compound at a
concentration 3 times greater than the MDL (Table 8). If the method blank did not meet these
criteria, the analytical system was out of control and the source of the
contamination was investigated and corrective measures taken and documented
before further sample analysis proceeded.
Internal standard analysis
For
organochlorine pesticides analysis, phenanthrene-d10 and perylene-d12 were used
as internal standards. For phenolic
compounds, bisphenol A-d14 was used as surrograte standard, and naphthalene-d8,
phenanthrene-d10 and perylene-d12 were used as internal standards. For phthalates, Di n-butyl phthalate-d4
(DBP-d4), Di 2-ethylhexyl phthalate-d4 (DEHP-d4) were used as internal
standards, and Di n-pentyl phthalate-d4(DPeP-d4) was used as surrogate
standard. The internal and/or surrogate
standard solution was spiked into the sample prior to extraction in an attempt
to compensate for individual sample matrix effects associated with sample preparation
and analysis. The laboratory took
corrective action whenever the recovery of the internal standard used to
quantitate was outside of the 60 to 140% range.
The following corrective action was taken when an out of control event
occurred:
Calculations
were checked to assure that no errors were made. The internal standard solutions were checked
for degradation, contamination, and other problems, and instrument performance
was checked. If the steps above failed
to reveal a problem, the sample or extract was reanalyzed. If reanalysis of the extract yielded internal
standard recoveries within the stated limits, then the reanalysis data was
reported. If QA criteria were still
violated upon reinjection, the sample was submitted for re-extraction.
GC resolution
The
target compounds, internal standard, and GC internal standard were resolved
from one another and from interfering compounds. When they were not, coelutions were
documented.
Recovery and
Reappearance Test
10 ng of each phthalate was added into seven real water samples (100 ml) and took the same preparation and analysis to check the recovery. The recovery of phthalates showed very good result and range was 96.4~121.7%(Table 9 & 10). CV was 4.2~13.7%.
2
ul of each phthalates standards (0.200ng/ml) were analyzed seven times by using
GC-MS to check the repeatability of analysis
(Table 11). It showed excellent
repeatability of analysis and range was 0.197~0.229 ng/ml. CV was from 1.0 to 4.8% except BBP (11.7%).
CRM
Sediment
CRM (CRM117-100) was purchased from R.T. Cooperation and analyzed for
phthalates (DEP, DBP and DEHP). CRM was
analyzed 10 times. The results should
agree within 65 to 135% of certified values.
The average of recovery of DEP was 113% and range was 72~128%(Table 12). The average of recovery of DBP was 103% and
range was 67~133%. The average of recovery of DEHP was 107% and
range was 70~130%. All the results were within 65 to 135% of
certified values.
3. 3. Problems Encountered
Because
of aging of GC-MS, it has been out of order frequently and it hindered routine
maintenance of the instrument. The PC
attached to GC-MS is an old model, so it’s speed is too slow to proper
treatment of chromatograms. It can be
easily mended by changing the old PC.
4. Conclusions
No organochlorine pesticides and
chlorophenols were detected in this study.
Alkylphenols and bisphenol-A were detected in summer and winter. The range of alkylphenols in summer and winter were 25~142 ng/L and 18~1392 ng/L respectively. 4-t-Butylphenol and Nonylphenol were dominant compounds among target alkylphenols. The range of bisphenol-A in summer and winter were 14~137 ng/L and 12~344 ng/L respectively.
The level of total phenolic compounds was generally
higher in summer than winter except Busan and
The level of bisphenol A showed very similar trend to
total phenols. The level was generally
higher in summer than winter except Busan and
Only
DBP and DEHP were detected among 11 target phthalates in summer and
winter. DEHP level was generally higher
than DBP level in summer and winter (Fig. 7 & 8). There was no special seasonal variation of
DBP levels (Fig. 9). But DEHP level in
summer was generally higher than in winter except Uljin (Fig. 10).
Fig. 1. Sampling sites of seawater
Fig. 2. Seasonal variation of phenolic compounds in seawater
Fig. 3. Comparison between alkylphenols and bisphenol-A in summer
Fig. 4. Comparison between alkylphenols and bisphenol-A in winter
Fig. 5. Seasonal variation of alkylphenols in seawater
Fig. 6. Seasonal variation of Bisphenol A in seawater
Fig. 7. Comparison between DBP and DEHP in summer
Fig. 8. Comparison between DBP and DEHP in winter
Fig. 9. Seasonal variation of DBP in seawater
Fig. 10. Seasonal variation of DEHP in seawater
Table
2. Concentrations of organochlorine pesticides from seawater in summer (ng/L)
|
Compounds |
Uljin |
|
|
Busan |
|
|
Kunsan |
Boryung |
Shihwa |
|
a"-HCH |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
|
b-HCH |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
|
g-HCH |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
|
d-HCH |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
|
Aldrine |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
|
Dieldrine |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
|
Endrin |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
|
p,p'-DDE |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
|
p,p'-DDD |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
|
p,p'-DDT |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
|
Total |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
Table
3. Concentrations of organochlorine pesticides from seawater in winter (ng/L)
|
Compounds |
Uljin |
|
|
Busan |
|
|
Kunsan |
Boryung |
Shihwa |
|
a"-HCH |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
|
b-HCH |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
|
g-HCH |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
|
d-HCH |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
|
Aldrine |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
|
Dieldrine |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
|
Endrin |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
|
p,p'-DDE |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
|
p,p'-DDD |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
|
p,p'-DDT |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
|
Total |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
Table
4. Concentrations of phenolic compounds
in summer (ng/L).
|
Analytes |
Uljin |
|
|
Busan |
|
|
Kunsan |
Boryung |
Shiwha |
|
4-n-Butylphenol |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
|
4-t-Butylphenol |
21 |
ND |
42 |
21 |
28 |
22 |
28 |
28 |
22 |
|
4-n-Pentylphenol |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
|
4-n-Hexylphenol |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
|
4-n-Heptylphenol |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
|
4-n-Octylphenol |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
|
4-t-Octylphenol |
ND |
ND |
10 |
10 |
11 |
11 |
13 |
11 |
13 |
|
Nonylphenol |
25 |
51 |
56 |
122 |
142 |
65 |
99 |
60 |
126 |
|
total APs |
46 |
51 |
108 |
153 |
181 |
98 |
140 |
99 |
161 |
|
2,4-Dichlorophenol |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
|
Pentachlorophenol |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
|
Total CPs |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
|
Bisphenol-A |
14 |
58 |
137 |
58 |
103 |
52 |
80 |
35 |
16 |
|
Total |
60 |
109 |
245 |
211 |
284 |
150 |
220 |
134 |
177 |
Table
5. Concentrations of phenolic compounds
in winter (ng/L).
|
Analytes |
Uljin |
|
|
Busan |
|
|
Kunsan |
Boryung |
Shiwha |
|
4-n-Butylphenol |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
|
4-t-Butylphenol |
ND |
7 |
6 |
110 |
18 |
5 |
7 |
7 |
13 |
|
4-n-Pentylphenol |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
|
4-n-Hexylphenol |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
|
4-n-Heptylphenol |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
|
4-n-Octylphenol |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
|
4-t-Octylphenol |
ND |
17 |
15 |
52 |
45 |
12 |
13 |
6 |
9 |
|
Nonylphenol |
18 |
35 |
63 |
1230 |
352 |
38 |
58 |
42 |
58 |
|
total APs |
18 |
59 |
84 |
1392 |
415 |
54 |
78 |
55 |
79 |
|
2,4-Dichlorophenol |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
|
Pentachlorophenol |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
|
Total CPs |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
|
Bisphenol-A |
13 |
39 |
25 |
344 |
156 |
31 |
40 |
26 |
12 |
|
Total |
31 |
98 |
109 |
1736 |
571 |
85 |
118 |
82 |
91 |
Table 6. Concentrations of phthalates in summer (ng/L).
|
Analytes |
Uljin |
|
|
Busan |
|
|
Kunsan |
Boryung |
Shiwha |
|
DBP |
ND |
10 |
ND |
50 |
16 |
59 |
59 |
ND |
- |
|
DEHP |
ND |
48 |
82 |
197 |
311 |
71 |
69 |
53 |
- |
|
DEP |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
- |
|
DprP |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
- |
|
DPP |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
- |
|
BBP |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
- |
|
DHexP |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
- |
|
DCHP |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
- |
|
DEHA |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
- |
Total |
ND |
58 |
82 |
247 |
327 |
130 |
128 |
53 |
- |
Table 7. Concentrations of phthalates in winter (ng/L).
|
Analytes |
Uljin |
|
|
Busan |
|
|
Kunsan |
Boryung |
Shiwha |
|
DBP |
ND |
40 |
ND |
9 |
122 |
ND |
56 |
ND |
15 |
|
DEHP |
17 |
27 |
38 |
57 |
182 |
29 |
60 |
35 |
105 |
|
DEP |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
|
DprP |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
|
DPP |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
|
BBP |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
|
DHexP |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
|
DCHP |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
|
DEHA |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
ND |
Total |
17 |
67 |
38 |
66 |
302 |
29 |
116 |
35 |
120 |