Transcript Persistent manufactured chemicals for non

Persistent manufactured chemicals
for non-pesticide applications and
persistent by-products of industrial and
combustion process
in China and Hong Kong
Ming H. Wong
Hong Kong Baptist University
GEF PDF-B Workshop, Jan 1999
Table of contents
1.
2.
3.
4.
5.
General background of China and Hong Kong.
The use of persistent organics in China and Hong Kong.
Case study – PCBs, PCDDs and PCDFs in China.
PAHs in China.
Total PCBs, PCDDs, PCDFs and PAHs in abiotic and biotic
samples from China, Taiwan and Hong Kong.
6. Case study – PCBs and PAHs in Hong Kong.
7. Polycyclic aromatic hydrocarbons in water and sediment of
South China River.
8. PCBs in freshwater fish and sediments collected from the
Pearl River Delta and Hong Kong.
9. Induction of Cytochrome P4501A1 gene expression in Tilapia
exposed to coastal sediment.
10. General conclusion.
1. General background of China and Hong Kong
Climate
- Subtropical, with cool dry winters and hot wet summers.
- Rainfall occurs predominantly in the summer, coinciding with the
highest air temperatures.
Population
- The Pearl River delta, with an area of 23270 km2 (Ma, 1994) and a
population of 15 million (Chan, 1995).
- Hong Kong with an area of 1,067 km2 and a population of over 6 million.
Industrialization
- Since the implementation of the economic reform and open door policy in
1978, the provinces of the South China take the lead.
- Organic discharge from the industries textile, plastic, printing, dying,
tannery, food, electroplating and paper production.
- Heavy industrial activities and residential population close to Victoria
Harbour, but also in the developing New Towns.
Pollution
Environmental policy and legislation in China are neither strict nor effectively enforced.
Pollutants from Guangzhou and Shenzhen are washed into Hong Kong’s
estuarine waters.
The quality of drinking water and local food supplies are affected.
2,000 major industrial factories and an estimated 200,000 smaller ones in Hong
Kong.
In Hong Kong, agricultural pollution from New Territories is due to rearing of
pigs and poultry, the populations of which are currently estimated to be 0.7
million and 7.5 million, respectively.
Hong Kong produces about 24,000 tonnes of solid wastes per day (HKEPD,
1995).
Since 3.5 million people and a large proportion of the industrial base are
concentrated around Victoria Harbour of Hong Kong. Sewage and industrial
effluents from these sources enter Victoria Harbour with little treatment
(Connell et al, 1998).
In Hong Kong, over 25% of the land in the urban area has been gained from
reclamation (Morton, 1989). The reduction in water area due to reclamation
has reduced the tidal flushing of both Victoria and Tolo Harbours, and
exacerbated the problems of pollution due to sewage discharges.
2. The use of persistent organics in China and Hong Kong
Table 1a. Manufactured persistent organic chemicals in China:
Heat Stabilizer
Major
Manufacturer
Use
Example
Dibasic Lead
Chemical Group
Phthalate
Use & Description
-
Phthalate
Shanghai
PVC
-
Heat
Stabilizer
electric resistant for
Location
heat and light
stabilizer for plastic
Pentachlorobiphenyl
PCBs
-
heat resistant for
plastic
-
flame retardant and
plasticizer
Shanghai
Table 1b. Manufactured persistent organic chemicals in China:
Plasticizer
Major
Use
Example
Dimethyl
Chemical Group
Use & Description
Manufacturer Location
Phthalate
-
plasticizer
Shanghai, Hunan
Phthalate
-
plasticizer for plastic, paint and
widely distributed in
rubber
China
plasticizer for PVC & rubber and
Jiangsu, Zhejiang
Phthalate (DMP)
Diisooctyl
Phthalate (DOP)
Butyl Benzyl
Plasticizer
Phthalate
-
Phthalate
use with other plasticizer
Chlorinated
Polychlorinated
-
plasticizer for PVC
Paraffin-42
Paraffin
-
additive for paint and lubricant oil
Chlorinated
Polychlorinated
-
plasticizer for PVC
Paraffin-52
Paraffin
-
additive for paint and lubricant oil
Diisoctyl m-
Phthalate
-
plasticizer
-
substitute for DOP
Phthalate
Shanghai, Guangzhou
Shanghai, Guangzhou
Tianjian
Table 1c. Manufactured persistent organic chemicals in China:
Flame Retardant
Major
Use
Example
Chemical Group
Decabromo Diphenyl
Polybromo
Ether (FR-10)
Diphenyl
Decabromodiphenyl Oxide
Polybromo
Use & Description
-
Manufacturer Location
flame retardant for PVC,
Jiangsu, Tianjian,
nylon, etc
Shangdong, Shanghai
-
flame retardant for plastic
Jiangsu
-
flame retardant for
Tianjian, Zhejiang,
plastic, rubber
Shanghai
flame retardant for
Shangdong, Shanghai,
plastic, rubber
Beijing
flame retardant and heat
Zhejiang
Diphenyl
Tetrabromo Bisphenol A
Tetrabromo Bisphenol A
Polybromo Phenol
Polybromo Phenol
-
Allyl Ether
Flame
1, 2 - Bis (2, 4, 6-Tribomo
Retardant
Phenoxy) Ethane (FR-3B)
Chloroparaffin-70
Polybromo Phenol
stabilizer for plastic
Polychlorinated
Paraffin
Tetrabromophthalic
-
-
flame retardant for
Shanghai, Shangdong,
plastic, paint & adhesive
Shenyang
Phthalate
flame retardant for plastic
Zhejiang
Polybromo Phenol
flame retardant for plastic
Jiangsu
Anhydride
Dibromocresyl Glycidyl
Ether
Table 2. Output of manufactured persistent organic chemicals in
China
Product
Plasticizer
Stabilizer for Plastic and
Rubber
Chemical
Dibutyl Phthalate
Dioctyl Phthalate
Dimethoxyethyl Phthalate
Butyl Benzyl Phthalate
Disodecyl Phthalate
Mixed Phthalate
Dicotyl-p-Phthalate
Chlorinated Paraffin
Dibasic Lead Phthalate &
Organometallic Stabilizer
1992 (tonnes)
73,989
153,171
49
313
1,770
228
12,269
43,787
4,595
1993 (tonnes)
85,151
139,162
42
467
220
211
6,505
40,189
4,635
References for Tables 1 & 2:
Wang, L. S., Hua Gong Chan Pin Zong Ji, Shanghai Science & Technology Publisher, China, 1997
Yu, Z. M., ZhongGuo Hua Gong Shang Pin Da Quan (Dian Wei Hei), ZhongGuo Wu Zi Chu Ban She, Beijing, China, 1993
Yu, Z. M. ZhongGuo Hua Gong Shang Pin Da Quan (Dian Wei Hei), ZhongGuo Wu Zi Chu Ban She, Beijing, China, 1991
Wu, W. Z., Schramn, K. W., Henkelmann, B., Yediler, A., & Kettrup, A., PCDD/Fs, PCBs, HCHs, and HCB in sediments
and soil of Ya-er lake in China: Results on residual levels and correlation to the organic carbon and the particle size,
Chemosphere, Vol. 34, No. 1, pp. 191-202, 1997
Jiang, K. Li, L. J., Chen, Y. D., & Jin, J., Determination of PCDD/Fs and Dioxin-like PCBs in Chinese commercial PCBs and
emissions from a testing PCB incineration, Chemosphere, Vol. 34, No. 5 - 7, pp. 941-950, 1997
Table 3. Import & export of persistent organic chemicals in Hong
Kong
Import Statistics
Commodities
Aromatic Cyclic Alcohols and their Halogenated,
Sulphonated, Nitrated or Nitrosated Derivatives
Halogenated, Sulphonated, Nitrated and Nitrosated
Derivatives of Phenols or Phenol-Alcohol
Unit
1993
1994
1995
1996
kg
1,062,493
1,343,189
1,533,794
1,562,531
Phthalic Anhydride
Dioctyl-o-Phthalates
Dimethyl-t-Phthalates
Insecticides
Compound Plasticizers for Rubber or Plastics
Liquid Dielectic Transformer
kg
758,776
950,525
kg
2,353,072 5,524,191
kg 61,357,396 90,387,720
kg
NA
16,000
kg 15,248,510 16,049,884
HK$
209,127
351,368
No.
47
510
Export Statistics
Commodities
Insecticides
Compound Plasticizers for Rubber or Plastics
Unit
kg
HK$
1993
NA
40,278
1994
4,082,026
NA
1,003,327
591,640
15,168,230
81,414
80,122,197 688,107
483,000
NA
16,556,661 12,544,204
668,319
652,260
499
10209
1995
NA
79,961
1996
3,934,040
52,995
References:
1) Hong Kong Trade Statistics - Import,1993 -1996, Census and Statistics Department, Hong Kong
2) Hong Kong Trade Statistics - Exports and Re-exports, 1993 -1996, Census and Statistics Department,
Hong Kong
Table 4. The order of high priority environmental pollutants of
China
Group
1. Halogenated
Methane /
Ethane
2. Benzene
3. Chlorinated
Benzene
4. Polychinated
Biphenyls
Name
Dichloromethane
Trichloromethane
Tetrachloromethane
1,2-Dichloroethane
1,1,1-Trichloroethane
1,1,2-Trichloroethane
1,1,2,2-Tetrachloroethane
Trichloroethylene
Tetrachloroethane
Tribromomethane
p-Xylene
Chlorobenzene
o-Dichlorobenzene
p-Dichlorobenzene
Hexachlorobenzene
PCBs
Acute Toxicity
LD50 (mg/kg)
2136
908
2800
678
5100
582
30
3670
3005
1147
3810
2910
670
500
10000
2000
Chronic Toxicity
TCLO (mg/kg)
Aquatic-life
Toxicity (mg/L)
/
/
/
/
/
/
/
/
/
/
/
10-100
1-100
/
/
/
/
20.1
43 (human)
1338
43
532
/
594
2100
1100
150
750
/
/
/
0.067 / day
Table 4. (cont.)
Group
5. Phenol
6.Nitrobenzen
7. Aniline
Name
Phenol
m-Cresol
2,4-Dichlorophenol
2,4,6-Trichlorophenol
Pentachlorophenol
p-Nitrophenol
p-Nitro-toluene
2,4-Dinitro-toluene
Trinitro-toluene
p-Nitrochlorobenzene
2,4-Dinitro-1-chlorobenzene
Aniline
Dinitroaniline
p-Nitroaniline
2,6-Dilchloro-1-nitroaniline
Acute Toxicity
LD50 (mg/kg)
317
242
580
820
27
250
1960
268
795
420
1070
250
418
750
1500 (oral-mice)
Chronic Toxicity
TCLO (mg/kg)
300
143
/
/
50
10
/
/
/
/
/
150
1.1
/
/
Aquatic-life
Toxicity (mg/L)
/
/
/
/
1
/
/
/
/
/
/
/
/
/
/
Table 4. (cont.)
Group
8. Polyaromatic
Hydrocarbon
9. Phthalate
10. Pesticides
11.Acrylonitrile
Name
Naphthalene
Fluoranthene
Benzo[b]fluoranthene
Benzo[k]fluoranthene
Benzo[a]pyrene
Indeno[1,2,3-c,d]pyrene
Benzo[g,h,i]perylene
Dimethyl-phthalate
Di-n-butyl-phthalate
Dioctyl-phthalate
Hexachloro-cyclohexane
DDT
DDV
Dimethoate
Parathion
Parathion-methyl
Nithofen
Trichorfon
Acrylonitrile
Acute Toxicity
LD50 (mg/kg)
1250 (oral-mice)
2000
/
/
50
/
/
6800
8000
6513
88
113
25
140
6
9
740
150
78
Chronic Toxicity
TCLO (mg/kg)
Aquatic-life
Toxicity (mg/L)
/
/
/
/
0.455
/
/
1125
140
5000
/
6
15
/
/
/
37.5
2.2
37.9
1-10
/
/
/
/
/
/
/
/
/
/
<1
/
/
/
/
/
/
/
Reference:
National Environmental Protection Agency, Database: Environmental Protection. Hebei Publisher, 1990
The use of persistent organics in China
and Hong Kong
Conclusion
1) Many manufactured persistent organic chemicals (eg. phthalate,
halowax, polybromophenol, etc.) are actively used in heat stabilizer,
plasticizer and flame retardant.
2) More than 200,000 tonnes and 40,000 tonnes of phthalate and halowax
are produced every year.
3) China produces about 5000 tonnes of Pentachlorophenol (PCP)
annually (Wu et al., 1997).
4) Environmental concerns on liquid dielectric transform are growing
owing to the existence of PCBs and PCB substitutes.
5) Input of persistent organic chemicals to HK is much more than
output.
3. Case Study – PCBs, PCDDs & PCDFs
in China
-
-
Industrial production started from 1965 and ceased at
1974
10,000 tonnes produced during that periods
Two different types of Chinese commercial PCBs –
PCB3 and PCB5, which are similar to Aroclor 1242
and 1254 respectively
Pentachlorobiphenyl is still applied as one of the
additives in the manufacture of paint today.
Starting from 1985, more than 2000 transforms have
been demolished.
•
•
Scientific Studies
Yang Y. H., Sheng G. Y., Fu J. M. & Min Y. S. Organochlorinated compounds
in waters of the Pearl River Delta region. Environmental Monitoring and
Assessment, 44, 567 – 575, 1997
Ranged from 0.80 to 9.23 g/L
Sewage water > river water
•
Chu S. G., Xu X. B., Fang Y. P., The distribution and environmental behaviour
of PCBs in classic polluted sites, Acta Scientia Circumstantiae, 15, 1, 1995
Bio-magnification in reference contaminated area
[PCBs] in water < sediment < fish
Bio-accumulation in fish
[PCBs] in muscle < bile < gallbladder < liver
•
Chu S. G., Xi Z. Q., Xu X. B, Polychlorinated Biphenyl (PCB)
Congeners in Mussel and other Mollusc from Da Chen Island, East
China Sea, Bull. Environ. Contam. Toxicol., 55, 682 – 688, 1995
Bio-concentration ranged from 1.40 to 9.34 g/kg
[PCBs] correlated with distance of sampling sites from the estuary
of the river.
•
Chu S., Xi Z., Xu X. Zhang Y., Xu Y, Induction of Micronuclei in
peripheral erythrocytes of Misgurnus anguillicaudatus by
polychlorinated biphenyls. Bull. Environ. Contam. Toxicol., 57, 179 182, 1996
Water polluted by PCBs have a possible mutagenicity of aquatic
organisms
Increase on the incidence of micronuclei with the increase of
[PCB3] and time exposure
Suitability of assessing peripheral blood of fish for the induction of
micronuclei as a short term test for monitoring
environmental genotoxicants

Xi Z. Q., Chu S. G., Xu X. B., Zhang Y. Y. Xu. Y., Fang Y.P., Li W.,
Effects of PCBs on the Electrolyte Balance in Blood of Crucian Carp,
Research Centre for Eco-Environmental Sciences, Academia Sinica,
Beijing, China, (in process)
Effect on dielectric concentration balance in the plasma of carp
[Na+] 
[K+] 
No observable change in [Ca2+] & [Mg2+]

Zheng M. H., Bao Z. C., Wang K. O., Xu X. B., Levels of PCDDs
and PCDFs in the Bleached Pulp from Chinese Pulp and Paper
Industry, Bull. Environ. Contam. Toxicol., 59, 90 – 93, 1997
PCDDs in pulp ranged from 140.0 to 390.5 pg/g dry pulp
PCDFs in pulp ranged from 7.3 to 80.4 pg/g dry pulp
•
Zheng M. H., Bao Z. C., Wang K. O., Xu X. B., Polychlorinated
Dibenzo – p Dioxins and Dibenzofurans in lake Sediments from
Chinese Schistosomiasis Area, Bull. Environ. Contam. Toxicol., 59,
653 – 656, 1997
Total PCDDs & PCDFs were 15760 ng/g and 2260 ng/g in NaPCP respectively
Levels of PCDDs & PCDFs in lake sediments ranged from 51 to
220 ng/g and 0.3 to 15 ng/g respectively
4. Case study - PAHs in China
Table 5. Benzo(a)pyrene concentration in China soil and
atmosphere from industrial and non-industrial area
Sampling
location
Industrial
area
Nonindustrial
area
Soil g/g
Wheat, corn field
Rice
Atmosphere g/100m3
Deposition
2
(100t/km
/month)
mean
n
17
mean
229.4 133.0
n
23
mean
179.785.5
n
20
8.76 4.81
164.0 62.4
16
0.8 0.7
18
3.6 2.9
21
0.5 0.04
27.0 11.9
Table 6. PAH concentrations at different diameter of suspended particulate in air
Particle
diameter
m
>7.0
7.0-3.3
3.3-2.0
2.0-1.1
1.1
Total
Particle
diameter
m
>7.0
7.0-3.3
3.3-2.0
2.0-1.1
1.1
Total
Pyrene
Chrysene
Benz(a)anthracene
Industrial
area
Residential
area
Rural
area
Industrial
area
Residential
area
Rural
area
Industrial
area
Residential
area
Rural
area
3.68
1.67
2.53
1.79
5.22
14.89
0.57
0.28
0.51
0.75
7.94
10.05
0.18
0.10
0.12
0.22
0.48
1.10
3.25
3.38
2.73
2.82
7.17
19.35
0.58
0.42
1.29
0.72
4.51
7.52
0.10
0.25
0.14
0.38
0.82
1.69
2.49
1.57
1.63
3.46
9.75
18.90
0.49
0.34
0.29
0.61
1.22
2.95
0.09
0.38
0.36
0.95
3.50
5.28
Perylene
Benzo(a)pyrene
Industri
al area
Resident
ial area
Rural
area
Industri
al area
Resident
ial area
Rural
area
14.26
20.57
6.21
31.90
41.73
114.67
4.86
1.08
1.16
3.30
33.09
43.49
0.94
2.33
1.20
2.28
5.96
12.71
2.04
2.24
1.49
3.39
6.75
15.91
0.92
0.75
0.77
0.80
3.08
6.32
0.46
0.70
0.55
0.64
3.06
5.41
Reference:
Liu, S. J. and Wu, Y. Carcinogenic polycyclic aromatic hydrocarbon in environment.
Environment Protection in China. 1995.
Case Study - PAHs in China
Conclusion
 The background values of benzo(a)pyrene ranged from 1.5-28
g/kg in soil.
 Benzo(a)pyrene levels in soils collected from cultivated field in
industrial area were 179-223 g/kg.
 More than 6 times higher than those in non-industrial area.
 Elevated benzo(a)pyrene levels in air of industrial area due to
combustion process.
 Particle size affects the absorption of PAH to suspended particles
in the atmosphere.
 94% PAH was associated with the particles smaller than 2.9 m.
 PAH containing particles could settle down in lung via respiration
 Pose a potential health problem to human beings.
5. Total PCBs, PCDDs, PCDFs and PAHs in abiotic and
biotic samples from China, Taiwan and Hong Kong
4
1
x
1
0
1
8
1
x
1
0
N/A
NN//AA
NN//AA
N/A
PCB(pb)
4
1
x
1
0
S
e
d
i
m
e
n
tW
a
t
e
r
B
r
e
a
s
t
m
i
l
k
B
i
o
t
aS
o
i
l
F
l
y
a
s
h
F
o
o
d
China
Taiwan
Hong Kong
Figure 1a. Mean concentration (ppb) of total PCBs in different
monitoring samples from China, Taiwan and Hong Kong.
4
1
x
1
0
1
NN//AA
NN//AA
NN//AA
NN//AA
NN//AA
N/A
PCD(pb)
4
1
x
1
0
8
1
x
1
0
S
e
d
i
m
e
n
tW
a
t
e
r
B
r
e
a
s
t
m
i
l
k
B
i
o
t
aS
o
i
l
F
l
y
a
s
h
F
o
o
d
China
Taiwan
Hong Kong
Figure 1b. Mean concentration (ppb) of total PCDDs in different
monitoring samples from China, Taiwan and Hong Kong.
4
1
x
1
0
1
NN//AA
N/A
N/A
NN//AA
N/A
NN//AA
NN//AA
PCDF(pb)
4
1
x
1
0
8
1
x
1
0
S
e
d
i
m
e
n
tW
a
t
e
r
B
r
e
a
s
t
m
i
l
k
B
i
o
t
a
S
o
i
l
F
l
y
a
s
h
F
o
o
d
China
Taiwan
Hong Kong
Figure 1c. Mean concentration (ppb) of total PCDFs in different
monitoring samples from China, Taiwan and Hong Kong.
4
1
x
1
0
1
N/A
N/A
NN//AA
NN//AA
NN//AA
NN//AA
N/A
PAH(pb)
4
1
x
1
0
8
1
x
1
0
S
e
d
i
m
e
n
tW
a
t
e
r
B
r
e
a
s
t
m
i
l
k
B
i
o
t
a
S
o
i
l
F
l
y
a
s
h
F
o
o
d
China
Taiwan
Hong Kong
Figure 1d. Mean concentration (ppb) of total PAHs in different
monitoring samples from China, Taiwan and Hong Kong.
Total PCBs, PCDDs, PCDFs and PAHs in abiotic and biotic
samples from China, Taiwan and Hong Kong
Conclusion

Distribution patterns of PCBs in sediments showed smaller spatial
variations.

In HK and Taiwan, total PCBs retained more in sediments than
that in China.

Only a few monitoring surveys are available on the PCDD, PCDF,
and PAH contamination in air, water, sediments of China.

Spatial distribution of such contamination is unclear.

Multi-compartment monitoring is essential to elucidate the
behavior and fate of persistent organic chemicals and to assess the
current status of contamination.
6. Case Study - Study of PCBs and PAHs in Hong Kong
Table 7. Concentrationsa of total PCBs and total PAHs in
sediments from Victoria Harbour (Connell et al., 1998).
tance
l PCBs
l PCBs
l PAHs
l PAHs
Units
g kg-1
(dw)
g kg-1
(ww)
mg Kg-1
(dw)
g Kg -1
(ww)
Harbour station
VS5
VS6
VS1
VS2
VS3
VS4
10
16
6.8
14
5.6
NA
25.5
(23.7)
12.7
10.2
(6.8)
12.6
NA
191
(104)
125
(126)
5.6
NA
14.0
NA
VS8
VS9
VS10
11
4.3
3.2
27
9.5
(8.3)
9.6
16.7
(13.9)
3.1
NA
9.0
(4.9)
1.20
14.5
(13.7)
68
78
(51)
336
167)
NA
139
(92)
135
(88)
3.9
VS14
Typhoon shelters
VS12 to VS14 &
Period
VS16 to VS20
38-81
1992b
ND-169
1995-1996c
454
ND-139
1992b
1159
(811)
ND-824
1995-1996c
ND = not detected; NA = not available; ww = wet weight; dw = dry weight.
a Means with standard deviations in parenthese where available.
b Hong et al., 1995.
c EPD, 1995 - 1996.
Reference:
Connell, D. W., Wu, R. S. S., Richardson, B. J., Leung, K., Lam, P. S. K., and Connell, P. A. Occurrence of persistent
organic contaminants and related substances in Hong Kong marine areas: an Overview. Marine Pollution Bulletin
36:376-384, 1998
Table 8. Concentrationsa of total PCBs in sediments collected in
Hong Kong marine areas (Water Control Zones) during
1995-1996b (Connell et al., 1998)
Zone
Deep Bay
Eastern Buffer
Junk Bay
Mirs Bayb
North Western
Port Shelter
Southern
Tolo Harbour
Western
S1
10.0(7.0)
6.25(2.5)
NA
6.75(3.5)
NA
12.6(11.5)c
5.25(0.5)
NA
10.5(4.5)
S2
8.75(3.5)
5.25(0.5)
9.0(2.7)
6.5(3.0)
6.7(2.0)
6.75(3.5)c
5.0(0)
7.0(2.6)
7.75(5.5)
S3
6.75(2.3)
33.0(27.4)c
NA
7.75(3.2)
7.0(2.8)
5.75(2.25)
5.5(1.0)
7.7(7.2)
NA
Stations
S4
15.5(16.6)
7.25(2.6)
NA
5.0(0)
7.25(3.8)
11.75(12.2)
8.3(5.7)
5.0(0)
NA
Average (SD)
S5
NA
NA
NA
5.0(0)
14.7(11.8)c
5.3(0.5)
8.25(3.9)
10.0(9.2)
NA
S6
NA
NA
NA
9.75(9.5)
9.75(4.2)
5.75(1.5)
5.0(0)
NA
NA
S7
NA
NA
NA
6.25(2.5)
NA
5.0(1.6)
16.0(1.6)c
15.25(16.6)c
NA
10.25(3.7)
12.9(13.3)
9.0(2.7)
6.7(1.5)
9.1(3.4)
7.5(3.2)
7.6(3.9)
8.99(3.9)
9.1(1.9)
NA = not available.
a g kg-1 wet weight with standard deviations in parentheses.
b EPD, 1995-1996.
c Typhoon shelters and sheltered anchorages.
d Mirs Bay Stations continued: S8 5.3(0.5); S9 6.6 (2.8); s10 5.0 (0); S11 7.6 (4.6); S12 6.3 (2.3); S13 4.6
(0.5); S14 6.6 (2.0); S15 8.5 (7.0); S16 6.0 (1.7); S17 9.0 (6.9).
Table 9. Concentrationsa of total PAHs in sediments collected in
Hong Kong marine areas (Water Control Zones) during
1995-1996b (Connell et al., 1998)
Zone
Deep Bay
Eastern Buffer
Junk Bay
Mirs Bayb
North Western
Port Shelter
Southern
Tolo Harbour
Western
S1
S2
S3
Stations
S4
231(213.7)
42(5.2)
45(9.9)
41(1.5)
NA
120(117.7)d
43(5.4)
NA
60(13.5)
64(29.1)
40(1.4)
NA
41(3.6)
62(19.7)
42(2.0)d
49(8.5)
40(2.1)
NA
51(15.3)
230(158.3)d
NA
40(1.4)
44(4.9)
43(5.3)
170(174.4)
40(2.1)
NA
47(13.1)
60(13.2)
NA
40(1.2)
49(9.9)
48(11.3)
104(53.6)
39(2.6)
NA
S5
S6
S7
Average
(SD)
NA
NA
NA
40(1.2)
125(51.9)d
40(1.15)
60(5.7)
41(2.6)
NA
NA
NA
NA
44(3.2)
61(28.1)
43(6.9)
41(2.8)
NA
NA
NA
NA
NA
40(1.4)
NA
51(11.8)
156(44.8)d
50(13.9)d
NA
98.8(88.9)
93.6(92.5)
45.5(9.9)
40.4(1.5)
68.6(32.6)
55.7(28.8)
89.5(55.0)
42.41(4.4)
58.1(3.4)
Human
populationc
(x 105)
3.68
2.32
0.82
0.23
3.86
0.48
2.62
7.10
3.95
NA = not available.
a g kg-1 wet weight with standard deviations in parentheses.
b EPD, 1995-1996.
c Typhoon shelters and sheltered anchorages.
d Mirs Bay Stations continued: S8 5.3(0.5); S9 6.6 (2.8); S10 5.0 (0); S11 7.6 (4.6); S12 6.3
(2.3); S13 4.6 (0.5); S14 6.6 (2.0); S15 8.5 (7.0); S16 6.0 (1.7); S17 9.0 (6.9).
Case Study - PCBs and PAHs in HK
Conclusion

Total PCBs and PAH in sediments have been monitored at 13 stations in
Victoria Harbour.

PCBs and PAHs in marine sediments at 66 stations in 10 water quality
zones in Hong Kong were collated and analysed between 1987 and
1996.

Contamination by the PCBs was lower than world wide standards (up to
25.5 g/kg wet weight).

Substantial petroleum contamination in Victoria Harbour sediments (up
to 116 g/kg wet weight)

Total PCBs and PAHs were widely distributed in Hong Kong sediments
(background concentrations of 5 to 9.8 g kg-1 and 40 to 60 g kg-1 wet
weight respectively).

Substantial contamination was found in typhoon shelters (total
PCBs up to 169 g kg-1 wet weight; total PAHs, up to 1159 g
kg-1 wet weight).

Much of the PCBs and PAHs due to industrial discharges and
stormwater run-off (trace concentration originating from road
ways, motor vehicle discharges, disposal of electrical equipment
and other items).

Sewage would also be expected to contain trace concentrations.

PAHs are probably of combustion origin and the levels in the
various water quality zones show an approximate relationship
with the size of the human population in the catchment.
7. Polycyclic aromatic hydrocarbons
in water and sediment of South China River
Study sites:
Pearl River, Deep Bay, Shenzhen River, Reservoir
(Control site), Hong Kong Rivers
Samples:
River water and sediments at 16 locations in Pearl
River Delta.
Analysis:
16 PAHs were investigated.
Figure 2. Map of South China showing the sampling locations of
sediment and water.
0
0
5
2
0
0
0
2
Pearl River
Deep Bay
0
0
5
1
(g/Kdrywt)
Shenzhen River
0
0
0
1
Control
0
0
5
Hong Kong Rivers
0
p
o
n
m
l
k
j
i
h
g
f
e
d
c
b
a
s
e
t
i
S
Figure 3a. Mean concentrations of total PAHs in
sediment of South China rivers.
6
5
Pearl River
Deep Bay
3
Shenzhen River
2
Control
1
Hong Kong Rivers
(g/L)
4
0
p
o
n
m
l
k
j
i
h
g
f
e
d
c
b
a
s
e
t
i
S
Figure 3b. Mean concentrations of total PAHs in surface
water of South China rivers
Table 10. Present results compared with Sediment Quality Criteria for organic
micro-pollutants (expressed in µg/kg)
Compound
Fluoranthene
Benzo(b)
fluoranthene
Benzo(k)
fluoranthene
Benzo(a)pyrene
Benzo(ghi)
perlene
Indeno (123cd)pyrene
Total PAH
(Sum 10)
Present study
Hong Kong and China guidelines
European guidelines
Pearl
Shenzhen Hong
HK
HK
HK
China
Dutch
UK target
River
River
Kong (Target A) (Trigger B) (Action C)
Intervention value
value
<10-280 <10-140 <10-459
1200
5250
7000
ND
ND
ND
<10-188 <10-52 <10-167
550
2250
3000
ND
ND
ND
<10-134
<10-33
<10-80
550
2250
3000
ND
ND
ND
<10-547
<10-148
<10-35
<10-27
<10-136
<10-120
200
200
2250
2250
3000
3000
ND
ND
ND
ND
ND
ND
<10-36
<10-35
<10-40
200
2250
3000
ND
ND
ND
455.251199.3
185.51674.25
142.271384.2
ND
ND
ND
ND
40000
1000
Target A – indicate the desired quality for fairly clean sediment; they slightly exceed but are close to the background levels.
Trigger B – indicate that moderate pollution occurs. The target values proposed equate to about 50% of the trigger levels.
Action C – indicate heavily polluted sites (Lau Wong, 1991).
Intervention Values are now available to identify “serious contamination” of soils, sludges and groundwaters and to indicate when
remediation is necessary.
- “Target Values” are specified to indicate desirable uncontaminated chemical contents of both soils and water.
-
References:
Contaminated Spoil Management Study. (1991). Final Report, Vol. 1. Mott MacDonald Hong Kong Ltd., Agreement CE 30/90.
Environmental Protection Department, Hong Kong Government.
Cairney, T. (1996). Contaminated Land Problems and Solutions.
Table 11. Present results compared with Water Quality Criteria for organic
micro-pollutants (expressed in µg/l)
Compound
Naphthalene
Anthracene
Phenanthrene
Fluoranthene
Benz(a)anthracene
Chrysen
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(a)pyrene
Benzo(ghi)perlene
Indeno (123-cd)pyrene
Total PAH (Sum 10)
Pearl River
<0.1-1.4
<0.1-0.1
<0.1-1.8
<0.1-0.2
<0.1-0.1
<0.1-0.2
<0.1
<0.1
<0.1
<0.1
<0.1
<0.1-2.934
Present study
Shenzhen
River
Hong Kong
<0.1-1.2
<0.1-0.5
<0.1-0.2
<0.1-0.2
<0.1-3.0
<0.1-4.3
<0.1-0.3
<0.1-0.2
<0.1
<0.1
<0.1-0.2
<0.1-0.3
<0.1
<0.1
<0.1
<0.1
<0.1
<0.1
<0.1
<0.1
<0.1
<0.1
0.1-2.942
<0.1-3.433
China guidelines
China
ND
ND
ND
ND
ND
ND
ND
ND
0.002
ND
ND
ND
European guidelines
UK
Dutch
target value
Intervention value
0.1
70
0.02
5
0.02
5
0.005
1
0.002
0.5
0.002
0.05
ND
ND
0.001
0.05
0.001
0.05
0.002
0.05
0.0004
0.05
ND
ND
Target A – indicate the desired quality for fairly clean sediment; they slightly exceed but are close to the background levels.
Trigger B – indicate that moderate pollution occurs. The target values proposed equate to about 50% of the trigger levels.
Action C – indicate heavily polluted sites.
Intervention Values are now available to identify “serious contamination” of soils, sludges and groundwaters and to indicate
when remediation is necessary.
- Target Values are specified to indicate desirable uncontaminated chemical contents of both soils and water.
-
Reference
Lu, R. (1995). Standards for domestic drinking water. Handbook of Regulations on Environmental Protection in China.
Polycyclic aromatic hydrocarbons
in water and sediment of South China river
Conclusion

Total PAHs in the different locations show wide variations.

Elevated levels of total PAHs in sediments (up to 2200 g/kg dry
wt.) and water (up to 5 g/L) were detected in some locations.

Elevated concentrations of PAHs are observed in location adjacent
to industrial area.

Significant PAH contamination was found to be due to
Benzo(a)pyrene and chrysene in sediment and water, respectively
(slightly exceed the recommended guidelines).
8. PCBs in freshwater fish and sediments collected from
the Pearl River Delta and Hong Kong.
Study sites:
Pearl River Delta:
fish ponds: Dongguan, Shunde, Nanhai, Zhongshan and
Shenzhen
Hong Kong:
Fish ponds: Au Tau, Mai Po and San Tin
Rivers: Shing Mun River, Lam Tsuen River and
Tai Po River
Samples: sediments and freshwater fish
Freshwater fish species: black bass, tilapia, common carp,
big head, silver carp and grass carp.
Table 12a. Concentrations of PCBs in sediments collected from
the Pearl River Delta and Hong Kong.
Sediment
pond sediment, Pearl River Delta
pond sediment, Hong Kong
river sediment, Hong Kong
river sediment, Hong Kong
Victoria Harbor
Tolo Harbor
PCBs
(ng/g dry wt)
<1
<1
43-461
12.7-46.0
3.2-81
5.0-15.3
References
present study
ibid
ibid
Chui et al. 1990
Hong et al. 1995
Connell et al.
1998
Table 12b. Concentrations of PCBs in fish flesh collected from the
Pearl River Delta and Hong Kong.
Fish flesh
pond fish, Pearl River Delta
pond fish, Hong Kong
Tilapia in river, Hong Kong
Tilapia and Mullet in Mai Po
Marshes
Public health guidelines for fishery products:
NEPA, China
US Food and Drugs Administration
US EPA
PCBs
(g/g wet wt)
0.0009-0.023
0.00030.0075
0.066-0.078
0.0025-0.017
References
present study
ibid
ibid
Liang et al. 1998
0.2
2
0.01
 If an adult weighing 70 kg consumed 6.5 g of fish every day with PCBs concentration greater than
0.01 g/g wet wt, for 70 years, the risk would correspond to one cancer death per 100,000 person.
Note: Data in the present study printed in bold-face exceeded the US EPD recommended guideline.
5
4
a
PCBs
a
b
3
b
2
c
1
0
black
bass
tilapia
big head
silver
carp
grass
carp
Figure 4. Bioaccumulation of PCBs in different fishes
PCBs in freshwater fish and sediments collected from
the Pearl River Delta and Hong Kong.
Conclusion
1.
PCBs levels in pond sediments were less than 1 ng/g (dry wt).
2.
PCBs concentrations in river sediments ranged from 43-461 ng/g (dry
wt), which were higher than the previous studies in relation to Shing
Mun River (12.7-46.0 ng/g dry wt, Chui et al. 1991), Tolo Harbour (5.015.3 ng/g wet wt, Connell et al. 1998) and Victoria Harbour (3.2-81 ng/g
dry wt, Hong et al. 1995).
3.
Although PCBs concentrations in fish flesh collected from fish ponds in
the Pearl River Delta and Hong Kong did not exceed the NEPA
maximum permissible limits (0.2 g/g wet wt), 16% of fish collected
from the Pearl River Delta and 100% of fish collected from the rivers in
Hong Kong exceeded the more stringent guidelines of US EPA (0.01
g/g wet wt).
4.
Factors affecting bio-accumulation of PCBs in fish.

Ecological niches: feeding habits affects PCBs
accumulation in freshwater fish cultured in
wastewater system at Au Tau.

Possible uptake pathways for sediment-sorbed PCBs
accumulated in tilapia: ingestion sediment and/or
contact with contaminated particles contributed to the
major uptake route rather than water.
9. Induction of Cytochrome P4501A1 Gene Expression in
Tilapia Exposed to Coastal Sediment
The Outline Method of Reverse-TranscriptasePolymerase-Chain-Reaction (RT-PCR)
Liver tissues
Total RNA
RT-PCR
Specific primers
for CYP1A1
PCR products
•The present method is very sensitive
in detecting CYP1A1 gene expression,
Agarose gel
electrophoresis which is specific to organic contaminants.
•The method is simple and rapid.
Marker
Control
PCB/3h
PCB/6h
PCB/12h
Sediment
exposure
~270 bp
Induction of CYP1A1 gene expression in fish liver tissues using RT-PCR..
Induction of Cytochrome P4501A1 gene expression
in Tilapia exposed to coastal sediment
Conclusion

Exposure of tilapia to the sediments of PCBs (i.p. injection)
induced CYP1A1 levels in the liver tissues.

The biomarker is highly sensitive to the organic pollutant.

This enables us to monitor trace organic contamination in
local waters.
General Conclusion

Only a few monitoring surveys are available on the flame
retardant, PCB substitute and phthalates contamination in
air, water, and sediment of China, although they are
manufactured and used.

The order of highly concern on persistent organic chemicals
is PCBs > PAH > phthalate > pesticides.

The data indicates that the sediments of China are
contaminated with a relatively high concentration of total
PAHs, as well as lower concentrations of total PCBs,
PCDDs and PCDFs.

Benzo(a)pyrene is mostly concerned PAH component in
China.

In Hong Kong the most concern persistent organic
chemicals are PCBs, PAH and pesticides.

Background concentrations of 5 to 9.8 g kg-1wet weight
of total PCBs and 40 to 60 g kg-1 wet weight of total
PAHs in Hong Kong marine sediment.

Elevated concentrations of PCBs and PAHs were found in
Victoria Harbour sediment in the range 9.56 to
25.5 g kg-1 and 66 to 116 g kg-1, respectively.

Substantial contamination was found in typhoon shelters
(total PCBs, up to 169 g kg-1 wet weight; total PAHs,
up to 115 g kg-1 wet weight).

Sediments in Hong Kong rivers contained PAH and PCB
concentrations of 194 to 2199 g kg-1 dry wt and 12.7 to
461 g kg-1 dry wt, respectively.

More monitoring work should be done to get a clear
geographical distribution of persistent organic chemicals
in our region.

Multi-compartment monitoring and bioaccumulation
assessment is essential to elucidate the behavior and fate
of persistent organics, also to assess the current status of
contamination.