NIMD Forum 2010 Distribution of Mercury and methylmercury ... · PDF fileDistribution of...
Transcript of NIMD Forum 2010 Distribution of Mercury and methylmercury ... · PDF fileDistribution of...
Distribution of Mercury
and methylmercury in South Korea
Ph.D. Young-Hee KIM
Chemicals Behaviors Research Division
NIMD Forum 2010
Talk Outline
Conclusion & Future Plan
Hg Mass Balance Study of Lake An-Dong
T-Hg & MeHg levels of Sediment and Fish
Mercury issues in S. Korea
Content
Title
1. Mercury issues in S. Korea
115 120 125 130 135 140 14525
30
35
40
45
50
50 150 250 350 450
0
100
200
300
400
500
National survey showed… (Ministry of Environment, Rep. of Korea 2005)
• The whole exposure of Korean is in safe, but about 25% adults showed
above RfD value. ( German HBM: 5 ppb, US EPA: 5.8 ppb)
SamplesBlood T-Hg
(ng/g)
Percentiles
50 th 75 th 90 th 95 th
Adult
Total (n=2,000) 4.34 4.65 6.89 9.35 11.69
Age
20-29 3.98 4.21 6.19 8.54 9.35
30-39 4.18 4.55 6.68 6.21 10.69
40-49 4.79 5.23 7.6 9.91 12.75
50-59 4.52 4.82 7.22 9.73 12.52
> 60 4.06 4.38 6.39 9.05 12.07
sexMale 5.01 5.33 7.98 10.16 12.75
Female 3.76 4.03 5.98 8.03 9.77
Children Total (n=2,000) 2.42 2.28 2.92 3.75 4.20
Mercury exposure level
(Kim et al, 2008)
1. Mercury issues in Korea
AP Dastoor, Y Laroque, Atmos Environ (2004)
Global Hg emission
Asia -the largest contributor of anthropogenic
atmospheric Hg > 50% of global emissions
Country Total (t)
1 China 825.2
2 India 171.9
3 USA 118.4
4 Russia 73.9
5 Indonesia 68.0
6 South Africa 43.1
7 Brazil 34.8
8 Australia 33.9
9 South Korea 32.2
10 Germany 30.0
Total 1,930
10 Largest Global Emitters of Hg (AMAP/UNEP, 2008)
1. Mercury issues in Korea
Mercury Emission Inventory of Korea
The contribution of mercury emissions varies depending on industrial characteristics in each country. (USA: Coal power plant (80%), China: Non-ferrous metal (45%), Japan: Waste incineration (37%))
Cement
production
4.1
13%
Steel
production
1.9
6%
Non-ferrous
metal
6.9
22%
Stationary
combustion
18.1
59%
(AMAP/UNEP, 2008)
1. Mercury issues in Korea
Transboundary Hg
SeoulLong-range transport
Local eventChina Japan Yellow sea North Korea
Event (N) 56 (62%) 3 (3%) 3(3%) 1 (1%) 27 (30%)
TGM Conc. (ng/m3) 5.28±2.74 4.51±1.60 3.56±1.17 5.50±1.40 4.80±1.72
China Japan
Yellow sea North Korea
• More than 50% of Hg
high events from
China by long-range
transport.
• ~30% of high event
from Local event.
(Han et al., 2009)
Launched National
human
biomonitoring
project from 2006
High fish
consumption and
high Hg level in
blood
Long-term &
intensive
monitoring for
mercury and
merthylmercury
Atmospheric Hg
monitoring program
(Launched from 2009)
Building Hg
Emission inventory
& Enhancement of
Hg emission criteria
Enforcement of
waste management
(Fluorescent lamp,
battery)
Emission Human HealthEco-system
Necessity of Hg monitoring in Ecosystem
Good Hg monitoring program is crucial: 1) to better
understand the biogeochemical cycling of Hg in the
environment; 2) to help enhance management and policy
development capabilities
1. Mercury issues in Korea
LOGO
2. T-Hg & MeHg levels of
Sediment, Fish in S. Korea
Analytical Methods for T-Hg & MeHg
Items Biological samples Soil/Sediment Water
Sample Amount
≥ 10 g 100 g 250 mL
Total Mercury DMA (EPA method 7473) DMA (EPA method 7473) CVAFS (EPA method 1631)
MethylmercuryKOH Digestion
GC-CVAFS (Modified EPA method 1630)
DistillationGC-CVAFS
(Modified EPA method 1630)
DistillationGC-CVAFS
(EPA method 1630)
3.2 환경모니터링 (수질,퇴적물, 생태)
Brooks Rand ⅢTekran 2600
GC-CVAFS (CETAC)DMA 80 (Milestone)
Distillation Clean Room (Class 10,000 )
11
Mercury & methylmercury in Sediment
River (46)Lake (12)Reservoir (9)Urban stream (5)Plant effluent (8)
Sediment sampling sites
(Jun. ~ Sep. 2007)
Sampling sitesT-Hg MeHg [GC-MS]
Average Range Average Range
Plant effluent 433.4±568.9 10.1~1564 1.78±1.97 N.D.~5.95
Urban stream 92.8±114.4 7.1~282.6 1.06±1.20 N.D.~2.78
River 1 (BOD<3) 53.5±62.4 2.7~251.6 1.37±1.15 N.D.~4.34
River 2 (BOD>3) 57.4±74.8 3.6~299.0 0.90±0.81 N.D.~3.44
Lake &Reservoir 27.7±20.9 2.4~70.8 0.94±0.99 N.D.~3.79
Total 98.4±232.7 2.4~1,564 1.16±1.17 N.D.~5.95
• T-Hg & MeHg in Sediment (ng/g, dry weight)
* MDL : 0.05 ngg-1
2. Hg levels in Sediment & Fish
12
[T-H
g]
(ng
/g)
0
100
200
300
400
500
[Me
Hg
] (n
g/g
)
0
1
2
3
4
5
%M
eH
g
0
2
4
6
8
10
[T-Hg]
[MeHg]
%MeHg
Plant
effluent
Urban
Stream
River 1
(BOD<3)
River 2
(BOD>3)Lake &
Reservoir
[T-H
g]
(ng
/g)
0
100
200
300
400
500
[Me
Hg
] (n
g/g
)
0
1
2
3
4
5
%M
eH
g
0
2
4
6
8
10
[T-Hg]
[MeHg]
%MeHg
Plant
effluent
Urban
Stream
River 1
(BOD<3)
River 2
(BOD>3)Lake &
Reservoir
0.01
0.1
1
10
100
1 10 100 1000 10000
[Hg] (ng/g)
[MeH
g]
(ng
/g)
Plant effluenturban streamRiver 1River 2lakeReservoir
Statistically significant correlation
(RT-Hg-MeHg=0.41, p<0.05),
A similar value (RT-Hg-MeHg=0.40) of
previous study (Benoit et al, 2003).
• %MeHg : 2.52±2.39% (n=68)
• The %MeHg in lake and
reservoir sites (3.27%) is high
compared to plant effluent
sites (0.86%) which is due to
high total Hg concentration in
plant sites.
2. Hg levels in Sediment & Fish
Sediment metal concentrations & correlations
Cr Ni Cu Zn Pb Fe(x100) Mn
[Meta
l] (
mg
/Kg
)
0
200
400
600
800
1000
1200
1400
1600
1800
Plant effluent
Urban stream
River 1
River 2
Lake&Reservoir
Parameter T-Hg MeHg %C %S
T-Hg 1 0.41 0.41 0.48
MeHg 0.41 1 0.28 NC
%C 0.41 0.28 1 0.67
%S 0.48 NC 0.67 1
Cr 0.39 NC 0.50 0.77
Ni 0.45 NC 0.62 0.89
Zn 0.67 NC 0.59 0.72
Pb 0.51 NC 0.65 0.91
Fe NC 0.29 NC NC
Mn NC NC NC NC
a. NC = no correlation
• Other metal concentrations of plant effluent sites were also relatively high
compared to those of other sites
• With T-Hg, all parameters showed significant correlation, but with MeHg,
no correlation were found.
2. Hg levels in Sediment & Fish
14
Methylmercury in Freshwater Fish
Freshwater Fish sampling sites
(Jun. ~ Sep. 2006)
Species No T-Hg MeHg
Mandarin fish 2 413.1±57.8 219.0±45.7
Korean piscivorous chub 5 357.9±75.7 254.2±68.2
Skin carp 4 220.4±90.3 206.1±159.9
Catfich 7 216.1±106.2 140.8±82.3
Skygager 6 191.8±117.6 175.7±118.7
Sharpbelly 1 153.4 77.0
Northern snake head 6 136.5±62.4 102.3±71.7
Bass 9 116.6±58.8 89.8±53.3
Carssius cuvieri 1 151.8 125.1
Crusian carp 2 59.9±3.0 42.9±0.7
Common carp 11 49.2±34.4 50.3±41.1
Leather carp 2 35.1±16.7 24.2±10.2
Japanese dace 1 183.16 141.4
Correlation between [T-Hg] and [MeHg]
y = 0.8789x - 1.7601
R2 = 0.787
0
100
200
300
400
500
0 100 200 300 400 500[T-Hg] (ng/g)
[MeH
g]
(ng
/g)
The proportion of methylmercury to total
mercury in all fish samples was in the range
of 69.1 ~ 103.5% indicated that majority of the
total mercury in fish is in the form of
methylmercury.
• T-Hg & MeHg in Freshwater fish (ng/g, wet weight)
2. Hg levels in Sediment & Fish
15
Fish weight Vs [MeHg]
0
100
200
300
400
500
0 500 1000 1500 2000
Weight (g)
[Me
Hg
] (n
g/g
)
Snake head (0.88)
Skygager (0.76)
Korean piscivorius chub (0.76)
Common carp (0.58)
Bass (-0.15)
Correlations between MeHg & fish weight
• MeHg concentrations and accumulation rates are increased with trophic level
and different species show different patterns.
• MeHg concentrations are significantly correlated with fish body weight (R =
0.58 ~ 0.88, p<0.05).
2. Hg levels in Sediment & Fish
16
Correlations between MeHg & fish weight (2)
0
50
100
150
200
100 200 300 400 500 600 700 800
weight (g)
[MeH
g]
(ng
/g)
Bass 1Bass 2
• Water quality of Ju-Nam and Dam-Yang reservoirs, 2002~2006
Dam-yang reservoir(Bass 2)
Ju-Nam reservoir(Bass 1)
ReservoirsTemp
(℃)pH
DO
(mg/L)
Cond.
(㎛hos/cm)
COD
(mg/L)
SS
(mg/L)
TN
(mg/L)
TP
(mg/L)
Chlorophyll A
(mg/m3)
Ju-Nam 17±1 7.6±0.2 8.5±0.6 210±25 7.6±0.5 11.5±4.0 1.28±0.24 0.07±0.02 21.7±8.0
Dam-Yang 13±2 7.5±0.3 9.2±0.8 64±15 2.5±0.4 2.0±0.6 1.65±0.71 0.04±0.01 6.0±4.0
National survey for Mercury in freshwater fish
BasinNo of
sites
No of
species
No of
samples
Han River 35 42 1,718
Geum River 11 23 394
Nak-dong River 30 42 998
Young-san River 16 30 600
Total 92 57 3,710
Freshwater Fish sampling sites
(2007~2008, Ministry of Environment)
2. Hg levels in Sediment & Fish
T-Hg in Freshwater fish
Fishes n LengthT-Hg
%MeHgAverage Range
mandarin fish 65 18.3 ± 4.1 173.1 ± 106.9 26.8 ~527 82.0
catfish 79 29.1 ± 7.2 136.2 ± 220.4 18.9 ~1527.6 74.5
snakehead 16 39.3 ± 8.8 109.2 ± 104.7 28.2~414.9 78.9
skin carp 41 20.3 ± 8.1 90.2 ± 77 17.3 ~ 336.7 72.7
Korean dark sleeper 48 11.0 ± 2.9 85.7 ± 99.8 14.5 ~ 480.4 78.8
Korean bullhead 143 15.0 ± 3.5 80.9 ± 63 3.9~ 428.7 75.4
striped shinner 80 10.6 ± 1.8 80.1 ± 49.1 7.5 ~ 279.6 88.1
Coreoperca herzi 87 10.3 ± 2.4 73.3 ± 71 7.4 ~ 424.9 74.4
long-nosed barbel 31 13.4 ± 1.4 66.1 ± 37.9 12.1 ~ 139.5 78.5
korean piscivorous chub 57 11.5 ± 3.5 60.8 ± 39.3 12.5 ~ 153.7 77.1
pale chub 160 10.3 ± 2.1 57.6 ± 35.4 6.9 ~ 189 85.1
crucian carp 226 16.1 ± 6.0 55.4 ± 50.9 4.9~446.2 83.9
bass 29 15.8 ± 7.6 50.6 ± 32.8 21.5~ 164.4 79.1
black bullhead 57 13.4 ± 4.0 44.6 ± 36.1 9.9~ 274.8 78.9
common carp 68 27.7 ± 11.3 38.8 ± 26.1 4.5 ~133.2 99.8
blue gill 88 9.8 ± 3.1 35.3 ± 15.8 9.3~ 73 82.7
goby minnow 44 13.7 ± 1.8 32.5 ± 19.1 3.8 ~ 89.5 83.0
Goby 104 18.2 ± 3.4 13 ± 11.2 0.4~ 55.8 95.4
2. Hg levels in Sediment & Fish
베스
0
500
1000
1500
2000
2500
3000
3500
4000
H-11
2H-11
N-14
H-6
K-8
2H-16
H-15
3H-1
Y-11
Y-4
H-7
Y-7
2H-4
H-14
3N-1
N-8
H-3-2
H-2
H-5
N-20
H-3-1
Y-6
Y-10
N-4
2Y-7d
Y-2
2N-21
2K-11
3H-2
2N-16
N-3
2N-17c
총수
은농
도(㎍
/㎏)
붕어
0
100
200
300
400
500
600
N-12
Y-8
N-7
N-17
2Y-7b
Y-11
N-13
2H-7
2H-8
2N-9
3H-1
H-8
N-9
H-18-2
K-1
N-14
Y-4
Y-9
N-3
Y-7
2Y-7d
2N-6
2K-15
H-17
2H-9
2N-1b
K-8
H-2
N-20
2H-11
N-4
N-1
2H-6
K-7
H-7
H-3-2
2H-4
H-3-3
H-18-1
H-5
Y-2
K-5
2H-14
2H-5
H-18-5
2Y-3
H-14
2H-15
2H-12
K-3
H-3-1
2N-17b
3H-2
H-16
2N-21
2Y-14
2K-12
2K-16
N-22
총수
은농
도(㎍
/㎏)
붕어
2H -8
2N -1a
2Y -7b
N -17
Y -7
0
50
100
150
200
250
300
350
400
450
500
0 10 20 30 40
길이(cm )
수은농
도(㎍
/㎏)
Site specific Correlations between T-Hg & fish size
베스
3H -1
3N -1
H -11
H -7
N -14
0
200
400
600
800
1000
1200
1400
0 10 20 30 40 50
길이(cm )
수은농도(㎍
/㎏)
Crucian Carp Bass
2. Hg levels in Sediment & Fish
Length(cm) Length(cm)
Sampling sitesSampling sites
T-H
g (
ng
/g)
T-H
g (
ng
/g)
T-H
g (
ng
/g)
T-H
g (
ng
/g)
National Map for Average Estimated Fish tissue concentration
- Under construction !
2. Hg levels in Sediment & Fish
Comparison of T-Hg between Natural and Farmed fish
1
10
100
1000
10000
1 10 100
길이 (cm)
총수
은 농
도 (
ug/k
g)
담수 어패류 (자연산)
담수 어패류 (양식산)
1
10
100
1000
1 10 100
길이 (cm)
총수
은 농
도 (
ug/k
g)
연근해 어패류 (자연산)
연근해 어패류 (양식산)
Length (cm)Length (cm)
T-H
g (
ug
/Kg
)
T-H
g (
ug
/Kg
)
Freshwater fish (Natural)
Freshwater fish (Farmed)
Shore fish (Natural)
Shore fish (Farmed)
Methylation Triggered by Fish farming practices?
- Methylation triggered by moderate levels of organic enrichment through fish
farming (Bay of Fundy, Vancouver) (Sunderland et al, 2006)
2. Hg levels in Sediment & Fish
SitesAverage T-Hg±SD
(ng/L)
Ranges
(ng/L)P Value
Total (n=300) 6.5±8.8 0.1~80.1
Han River (n=89) 8.1±11.4 0.1~80.1
0.599Nak-dong River (n=101) 6.1±7.8 0.1~57.3
Geum River (n=52) 5.4±6.8 0.1~25.9
Young-san River (n=58) 5.4±7.4 0.2~28.4
SitesAverage T-Hg±SD
(ng/L)
Ranges
(ng/L)P Value
River (n=197) 5.1±6.2 0.1~31.3
0.036Lake (n=84) 8.1±11.7 0.1~80.1
Reservoir (n=19) 13.2±13.1 1.3~57.3
Total Mercury in Freshwater
2. Hg levels in Sediment & Fish
SitesAverage T-Hg±SD
(ng/g, dry wt.)
Ranges
(ng/g, dry wt.)P Value
Total (n=290) 27.0±41.0 0.1~282.5
Han River (n=82) 29.6±36.6 0.1~170.3
0.599Nak-dong River (n=95) 30.3±49.7 0.8~282.5
Geum River (n=58) 23.6±35.4 0.3~146.1
Young-san River (n=57) 22.8±39.1 0.2~227.2
SitesAverage T-Hg±SD
(ng/g. dry wt.)
Ranges
(ng/g, dry wt.)P Value
River (n=188) 22.5±39.9 0.1~282.5
0.036Lake (n=80) 36.3±44.2 0.4~227.2
Reservoir (n=22) 31.1±33.1 3.0~100.6
Total Mercury in Sediment
2. Hg levels in Sediment & Fish
폐광지역
Zinc Smelter
Lake An-dong
50 km
Abandoned mines
Study site – Lake An-dong
3. Study of Lake An-dong
Lake An-dong
Lake An-dong
Lake Im-ha
Zinc Smelter
26
Zinc
smelter
Lake An-dong
Lake Im-ha
3. Study of Lake An-dong
Watershed of Lake An-dong & Im-ha
Elevation level (m)
(MOE,‘08)Lake An-dong Lake Im-ha
Korean Bullhead
강준치
0
500
1000
1500
2000
2500
N-14
3N-1
H-3-1
N-3
2H-6
H-3-2
N-1
H-5
H-15
N-4
K-1
K-7
H-17
H-2
2N-17b
H-1
H-3-3
3H-2
총수은
농도(㎍
/㎏)
블루길
0
100
200
300
400
500
600
N-14
K-8
Y-4
H-17
2H-12
Y-7
H-15
2Y-7d
H-1
3N-1
N-4
N-20
H-5
K-5
H-3-1
N-18
N-1
H-3-2
N-19
2H-15
Y-2
2K-11
H-3-3
2H-14
2N-21
N-3
3H-2
총수은
농도(㎍
/㎏)
Blue GillSkygager
베스
0
500
1000
1500
2000
2500
3000
3500
4000
H-11
2H-11
N-14
H-6
K-8
2H-16
H-15
3H-1
Y-11
Y-4
H-7
Y-7
2H-4
H-14
3N-1
N-8
H-3-2
H-2
H-5
N-20
H-3-1
Y-6
Y-10
N-4
2Y-7d
Y-2
2N-21
2K-11
3H-2
2N-16
N-3
2N-17c
총수
은농
도(㎍
/㎏)
Largemouth Bass
T-Hg in Freshwater Fish in Lake An-dong
3. Study of Lake An-dong
28
Wet deposition Dry deposition
Diffusion
Sedimentation
Resuspension
River outflow
Sediment outflow
River inflow
Evasion Evasion
Wet & Dry deposition
Atmospheric transport
Run-offThrough fall Litter fall
Groundwater exchange
Soil water
SOIL
PLANT
WATER
BIOTA
AIR(TGM,RGM, pHg)
Input & Output
Hg Mass Balance Study in Lake An-dong
3. Study of Lake An-dong
0.0430.735
6.3957.174
0
2
4
6
8
10
12
Hgp Hg+2 Hg0 HgT
Hg emission (Roasting, ㎍/m3)
1%
Hg emission Characteristic of Zinc smelter
• Missing input or
overestimated
output needs to
be re-estimated!
• Mainly emitted as
Hg(0) form
Hg Mass Balance of Zinc smelter
3. Study of Lake An-dong
1
Atmospheric Soil Plant
Jae-san
0
1
2
3
010203040
0
0.03
0.06
0.09
0
20
40
60
80
TGM
(1 ng/m3)
RGM Hgp
(10 pg/m3)
20 ug/kg
Chun-yang
Suk-po (Zinc smelter)
Chung-gi
Ye-An (super site)Buk-hu
(0.03mg/kg)
Sampling sites
(Air, Soil & Plant)
Periods
An-dong
Temp (℃) Wind speed (m/s) Rel. Hum. (%) Precipitation (mm)
Spring
(‘09.5.16~20)16.5 1.7 66.7 35.6
Summer
(‘09.7.20~24)24.9 1.6 75.6 129.5
Fall
(‘09.10.29~11.2)12.9 1.9 67.9 5.6
Meteorological condition
• Main Wind direction: Northwest
3. Study of Lake An-dong
0
100
200
300
400
500
1 2 3 4 5 6 7 8 9 10 11 12
월강
우량
(㎜
)
안동관측소
봉화관측소
태백관측소
Pre
cip
itati
on
(mm
)Month
Atmospheric Hg sampler
CVAFS(TEKRAN 2537/1130/1135) - Continuous
Dry deposition plate & Precipitation sampler NSA 181/KE
3. Study of Lake An-dong
• Hg sampler for TGM, RGM, Hgp
• Sampler for Dry & Wet deposition (Ye-An site)
Manual (Gold trap, denuder, quartz filter)
1
Atmospheric Soil Plant
Jae-san
0
0.03
0.06
0.09
020406080
0
1
2
3
010203040
0
0.03
0.06
0.09
0
20
40
60
80
TGM
(1 ng/m3)
RGM Hgp
(10 pg/m3)
20 ug/kg
Chun-yang
Suk-po (Zinc smelter)
Chung-gi
Ye-An (super site)Buk-hu
(0.03mg/kg)
Sampling sites
(Air, Soil & Plant)
34
TGM (Total Gaseous Mercury) concentrations
Country City Measurement periodAverage
(ng/m3)Reference
Korea
Andong(Yean)
2009. 5.15 ~ 5.20 2.92 ± 0.59
This study2009. 7.20 ~ 7.24 1.56 ± 0.29
2009. 10.29 ~ 11.2 1.80 ± 0.33
Seoul 1999-2000 5.34
China
Beijing 1998 8.3-24.7 Liu et al.(2002)
Changchun 1999-2000 18.4 Fang et al.(2004)
Guiyang 2001-2002 8.4 Feng et al.(2003)
Japan Tokyo 2000-2001 2.7 Satata et al.(2002)
USA
East Hartford 1997-1999 2.19-2.69 Nadim et al.(2001)
Chicago 1994-1995 3.6 Landis et al.(2002)
Detroit 1999-2002 1.17-40.33 Lynam and Keeler (2004)
New York 2000 3.84 Carpi and Chen (2002)
Canada Toronto 2001-2002 2.48 Denis et al.(2006)
Comparison of TGM concentrations
3. Study of Lake An-dong
35
RGM concentrations
HgP concentrations
Country City Measurement period RGM (ng/m3) Reference
KoreaAndong(Yean)
2009. 5.15 ~ 5.20 0.024 ± 0.003
This study2009. 7.20 ~ 7.24 0.040 ± 0.008
2009. 10.29 ~ 11.2 0.013 ± 0.011
Seoul 2006. 5 ~ 2007.10 0.007 ~ 0.017 Nier (2007)
JapanOkinawa
Hedo Station2004. 3.23 ~ 5.2 0.004 Daniel Jaffe et al. (2005)
USA
Tuscaloosa,
Alabama2003. 6.25 ~ 7.29 0.014±0.020 Mark C. Gabriel et al.
(2005)Cove Mountain, Tennessee 2002. 8.12 ~ 9.16 0.014±0.007
Country City Measurement period Hgp (ng/m3) Reference
KoreaAndong(Yean)
2009. 5.15 ~ 5.20 0.027 ± 0.004
This study2009.7.20 ~ 7.24 0.049 ± 0.013
2009. 10.29 ~ 11.2 0.019 ± 0.010
Seoul 2006.5 ~ 2007.10 0.014~0.089 Nier (2007)
Japan Tokyo 2000.4 ~ 2001.3 0.098 Masahiri et al.(2002)
USA Tuscaloosa 2003.6.25 ~ 2003.7.29 0.016±0.0195 Mark C. Gabriel et al. (2005)
Comparison of RGM & HgP concentrations
3. Study of Lake An-dong
36
Spring
Date
12:00 12:00 12:00 12:00 12:005/15 5/16 5/17 5/18 5/19 5/20
TG
M (
ng
/m3
)
0
1
2
3
4
5
RG
M (
pg
/m3
), H
gP
(p
g/m
3)
0
20
40
60
80
100
120
140
160
TGM
RGM
HgP
Summer
Date
12:00 12:00 12:00 12:00 12:007/20 7/21 7/22 7/23 7/24 7/25
TG
M (
ng
/m3
)
0
1
2
3
4
5
RG
M (
pg
/m3
), H
gP
(p
g/m
3)
0
20
40
60
80
100
120
140
160
TGM
RGM
HgP
Fall
Date
12:00 12:00 12:00 12:00 12:00 12:0010/30 10/31 11/1 11/2 11/3
TG
M (
ng
/m3
)
0
1
2
3
4
5
RG
M (
pg
/m3
), H
gP
(p
g/m
3)
0
20
40
60
80
100
120
140
160
TGM
RGM
HgP
Date
05/15/09 05/17/09 05/19/09
TG
M (
ng
/m3
), C
O(p
pb
)*0
.1
0
5
10
15
20
PM
10
(u
g/m
3),
O3
(p
pb
),
NO
2 (
pp
b)
0
20
40
60
80
100
120
140
TGM
PM10
NO2
O3
CO
Spring
Date
07/20/09 07/22/09 07/24/09
TG
M (
ng
/m3
), C
O(p
pb
)*0
.1
0
5
10
15
20
PM
10 (
ug
/m3),
O3 (
pp
b),
NO
2 (
pp
b)
0
20
40
60
80
100
120
140
Summer TGM
PM10
NO2
O3
CO
Date
10/30/09 10/31/09 11/01/09 11/02/09 11/03/09
TG
M (
ng
/m3
), C
O(p
pm
)
0
5
10
15
20
PM
10
(u
g/m
3),
O3
(p
pb
), N
O2
(p
pb
)
0
20
40
60
80
100
120
140
TGM
PM10
NO2
O3
CO
Fall
3. Study of Lake An-dong
Comparison of atmospheric Hg concentrations
Items 1 2 3 4 Ave. ± SD Max
Dry deposition (ng/m2∙day)
(This study, 2009. 11)4.404 6.732 4.282 5.744 5.29 ± 1.17 6.73
Wet deposition (ng/L)
(This study, 2009. 11)3.715 3.743 3.307 - 3.59 ± 0.24 6.80
Masahiro sakata et al., 2005
(ug/m2∙yr)
Dry 12.8 ± 3.92002. 12 ~ 2003. 11 (Japan)
Precipitation : 1626 ± 422 mmWet 8.0 ± 2.7
Gerald J. Keeler et al., 2009
(ug/m2 ∙ day)Wet 0.02 ~ 0.18
1995 ~ 2006, daily event (USA)
Precipitation : 4 ~ 16 mm
Peter F. Nelson et al., 2009
(ug/m2 ∙ day)
Wet 0.003 ~ 0.262
(1 ~ 19 ng/L)
2006. 6 ~ 2007. 12 (Australia)
Precipitation : 60 ~ 94 mm
3. Study of Lake An-dong
Comparison of Dry & Wet deposition flux
St.1
St.2
St.3 (After Zinc smelter)
Lake 5m Lake10mSurface water
1
Water
T-Hg(F) T-Hg
(ng/L)
Zn Cd
( ug/L)
Fish
Ave. Zacco
Koreanus
(mg/kg)
Piscivor
-ousMay Aug.
(mg/kg)
Invertebrate
St.4
St.5
St.6St.7
St.8-1
St.8-2
St.8-3
Sharpbe
lly
Sampling sites (Water, Fish & Microinvertebrates)
St.8-4
St.8-5
39
1 2
3
4 5
6 987
1 2
3
4 5
6 987
(Sampling in May & August, 2009)
108.8
406.4
93.468.52 64.7 57.551.1
156.0
37.6 45.7 34.2
St. 2 St. 3 St.4 St.5 St.6 St.7
T-Hg (ng/g dry weight)
May August
81.2
62.1
47.8
23.7
33.0
43.6
21.0 15.7
22.1
8.7
19.6
St.2 St.3 St.4 St.5 St.6 St.7
MeHg (ng/g dry weight)
May August
Hg in Microinvertebrates
(After Zinc smelter)
74.6
15.3
51.1
34.5
51.0
75.9
41.1
10.0
58.8
19.0
57.3
St.2 St.3 St.4 St.5 St.6 St.7
May(%MeHg) Aug(%MeHg)
T-Hg in Freshwater Fish
Species No. T-Hg ±SD
(ng/g, wet wt.)
Ranges
(ng/g, wet wt.)
dark chub 8 31 ± 19 18~77
Coreoperca herzi 7 39 ± 28 12~92
stripped shiner 6 28 ± 13 11~43
goby minnow 6 21 ± 16 10~52
Cyprinidae 158 46 ± 21 17~147
Cobitis multifasciata 17 28 ± 11 15~53
Coreoleuciscus splendidus 11 61 ± 37 16~161
Barbatula toni 15 38 ± 16 19~66
Zacco Koreanus 39 38 ± 26 17~153
Long-nosed barbel 45 121 ± 39 12~207
Korean bleak 12 115 ± 93 28~393
Korean torrent catfish 11 48 ± 41 21~165
Psle club 55 33 ± 24 12~116
Culter Brevicauda 21 123 ± 44 74~282
Piscivorous club 25 198 ± 97 125~611
Bass 5 100 ± 39 37~135
Blue gill 11 101 ± 48 47~174
Sharpbelly 41 156 ± 46 63~268
Total 511 72.8 ± 62.9 11~611
0
5
10
15
20
0
50
100
150
200
250
sharp
belly
Kore
an b
leak
Long-n
osed
barb
el
Pis
civ
oro
us
clu
b Bass
Blu
e g
ill
Length
(cm
)
T-H
g (
ng/g
)
Species from Lake
Average T-Hg Lake An-dong
Length(Average) Length(An-dong)
0
5
10
15
20
0
20
40
60
80
100
goby m
innow
Core
ole
ucis
cus
sple
ndid
us
Psle
clu
b
Cobitis
m
ultifascia
ta
str
ipped
shin
er
Length
(cm
)
T-H
g (
ng/g
)
Species from River
Average T-Hg Lake An-dong
Length(Average) Length(An-dong)
3. Study of Lake An-dong
0
100
200
300
400
0 10 20 30
T-H
g(n
g/g
, w
et
wt.
)
Length (cm)
끄리
백조어
버들개
참갈겨니
참마자
치리
피라미
Piscivorous club
Culter Brevicauda
Cyprinidae
Zacco Koreanus
Long-nosed barbel
Sharpbelly
Psle club
y = 8.591x - 29.178R² = 0.9713
y = 31.49x - 151.16R² = 0.8872
y = 10.938x - 46.604R² = 0.5748
0
20
40
60
80
100
120
140
0 5 10 15 20
T-H
g(n
g/g
)
Length (cm)
Psle club
성황교
제련소
임기
명호
고산정
도산서원
St.2
St.3
St.4
St.5
St.6
St.7
0
100
200
300
0 10 20 30
T-H
g(n
g/g
)
Length (cm)
Sharpbelly
도산서원
서부리
계곡리
St.8-1
St.8-2
St.8-3
Correlations between T-Hg & Length of fish
3. Study of Lake An-dong
Fall Fall (F)
Summer Summer (F)
Spring Spring(F)
0
1
2
3
4
5
6
표층 5m 10m
T-H
g(n
g/L
)
0m
T-Hg & Dissolved T-Hg of Lake water by depth
Concentrations of Dissolved gaseous mercury in Lake water
0
0.2
0.4
0.6
0.8
1
1.2
1.4
0 20 40 60 80
DG
M(n
g/L
)
Minutes
8h
13h
SitesT-Hg
(ng/L)
DGM
(ng/L)Period
Temp.
(℃)Ref.
An-dong 2.88 0.015 ‘09.11 17.0 This study
Ju-Nam - 0.093 ‘05.8 26.3 Oh, et al(‘06)
West Lake 5.01 0.076 ‘01.6 21.5 O’Driscoll(‘03)
Cane creek <0.2 0.041 ‘03.7 26 Dill et al(‘05)
T-Hg & DGM in water of Lake An-dong
3. Study of Lake An-dong
MeHg (ng/g) & %MeHg
0 2 4 6 8 10
Dep
th (
cm)
0
5
10
15
20
25
30
T-Hg(ng/g)
0 100 200 300
MeHg
%MeHg
T-Hg
MeHg (ng/g) & %MeHg
0 2 4 6 8 10
Dep
th (
cm)
0
5
10
15
20
25
30
T-Hg(ng/g)
0 100 200 300
MeHg
%MeHg
T-Hg
MeHg (ng/g) & %MeHg
0 2 4 6 8 10
Dep
th (
cm)
0
5
10
15
20
25
30
T-Hg(ng/g)
0 50 100 150 200 250 300
MeHg
%MeHg
T-Hg
• T-Hg : 155.0±71.9 ng/g (72.1~309.2 ng/g)
MeHg : 1.85±1.09 ng/g (0.12~4.32 ng/g)
% MeHg : 1.17±0.39% (0.69~2.09%)
• T-Hg in Sediment, S. Korea (’07, n=210)
- 27.0±41.9ng/g (0.1~282.5 ng/g)
• Lake Michigan (’04, US EPA n=118)
- 78±65 ng/g (0.002~260 ng/g)
Hg profiles of sediment in Lake An-dong
3. Study of Lake An-dong
St.8-5
St.8-4
St.8-1
y = 0.49x - 0.2237R² = 0.8256
0
0.5
1
1.5
2
2.5
3
3.5
0 2 4 6 8
Fit
ere
d T
-Hg
(ng
/L)
T-Hg(ng/L)
T-Hg Vs Dissolved Hg
y = 297.75x + 65.975R² = 0.7203
0
500
1000
1500
2000
2500
3000
0 2 4 6 8
Fe (
ng
/L)
T-Hg(ng/L)
T-Hg Vs Fe
0
0.5
1
1.5
2
2.5
3
3.5
4
0 2 4 6 8
Fit
ere
d T
-Hg
(ng
/L)
T-Hg(ng/L)
T-Hg Vs DOC T-Hg Vs Suspended solid
Correlations of T-Hg in water
3. Study of Lake An-dong
Analytes THg MeHg LOI Pb Zn Mn
THg 1.000 0.840 0.408* 0.830 0.372* 0.411
MeHg 0.840 1.000 0.583 0.661 NC NC
LOI 0.408* 0.583 1.000 NC NC 0.665
Pb 0.830 0.661 NC 1.000 0.564 0.335*
Zn 0.372* NC NC 0.564 1.000 0.596
Mn 0.411 NC 0.665 0.335* 0.596 1.000
Correlations of T-Hg in sediment
y = 0.3814x + 7.8995R² = 0.6961
0
20
40
60
80
100
120
140
160
180
0 100 200 300 400
Pb
(mg
/kg
)
Hg(ng/g)
T-Hg & Pb
y = 0.0124x - 0.0779R² = 0.6667
0
1
2
3
4
5
0 100 200 300 400
MeH
g(n
g/g
)
T-Hg(ng/g)
T-Hg & MeHg
* p<0.05, others p<0.01
y = 25.229x - 129.54R² = 0.2584
0
50
100
150
200
250
300
350
6 11 16 21T
-Hg
(ng
/g)
LOI(%)
T-Hg & LOI(%)
(Tokyo Bay, Japan) (Lake Michigan, Chicago)
Atmospheric input
0.29 kg/yr
0.099(dry), 0.19(wet)
Evasion
0.22 kg/yr
River output
2.22 kg/yr
Sedimentation
10.0 kg/yr
River input
1.59 kg/yr Storage(water)
1.51 kg/yr
Missing Input
9.05 kg/yr
Atmospheric input
0.29 kg/yr
0.099(dry), 0.19(wet)
Evasion
0.22 kg/yr
River output
2.22 kg/yr
Sedimentation
10.0 kg/yr
River input
1.59 kg/yr Storage(water)
1.51 kg/yr
Missing Input
9.05 kg/yr
Re-estimation
Hg Mass balance of Lake An-dong
3. Study of Lake An-dong
47
Conclusion & Future plan
Hg concentrations of sediment and freshwater fish in S. Korea were not so
high compared to high Hg level in blood and Hg emission.
Hg emission from the zinc smelter was low but some high concentrations of
soil, plant and microinvertbrates have been found near to the smelter.
The main Hg input source to Lake An-dong was river input (1.59 kg/yr) rather
than atmospheric input (0.29 kg/yr). Most of Hg is removed by sedimentation
(10.0 kg/yr).
The missing inputs of Hg mass balance (9.05 kg/yr) might be originated from
storm water input and tributary input. Soil discharged into stormwater run off
might be the major source of Hg in Lake An-dong. Need more intensive
monitoring for figuring out the mass balance budgets!
4. Conclusion
Acknowledgement
Dr. H. Akagi
Eun-Hee Kim (Jun-Nam Univ.)
Jong-Hyun Lee (NeoEnbiz)
49
Thank You !
DiffusionResuspension
Influent
습식침적
Dry depositionEvasion
Lake water
Effluent
Annual sedimentation amountⅹAv.T-Hg of sedimentⅹsurface area
0.13g/cm2·yr ⅹ 155ng/g ⅹ51.5km2
Sedimentation
T-Hg of st.7ⅹAnnual influent amount
2.59ng/L ⅹ 19.5m3/s
Water-gas exchange rate ⅹDGMⅹsurface area of Lake
0.8m/d ⅹ 14.9pg/L ⅹ51.5km2
Dry deposition flux ⅹSurface area of lake
1.9ug/m2 ·yr ⅹ 51.5km2
Conc. Precipitation ⅹAnnual precipitation ⅹSurface area of Lake
3.58ng/L ⅹ 1037mm ⅹ51.5km2
Av. containmentⅹT-Hg of St.8
621m3 ⅹ 2.44ng/L
T-Hg of st.8ⅹAnnual effluent amount
2.44ng/L ⅹ 28.9m3/s
Wet deposition
Estimation of Hg Mass balance
T-Hg & MeHg in Sediment (2)
T-Hg (ng/g) & %MeHg
0 2 4 6 8
Dep
th (
cm
)
0
2
4
6
8
10
MeHg (ng/g)0.0 0.1 0.2 0.3 0.4
T-Hg
%MeHg
MeHg
%Methylation/day
0 2 4 6 8 10 12 14
De
pth
(c
m)
0
2
4
6
8
10
%AVS/day1 2 3 4
%Methylation
%AVS
203HgLn
1cm
• Injected 203HgLn & Na235SO4 to the sediment from Tae-An
- 35.43 ng 203HgCl2 per 2cm & 2.1 nmol 35SO42- per 2cm
• Incubated for 4 hours, Extracted and Counted α, ß activities
Sediment Depth Profile (Tae-An) Methylation & AVS formation potential
52
Methylmercury in blood of children
Author Region Sample Mean of T-Hg (㎍L-1)
This studyRepublic of
Korea85 children aged 10-12 years
2.57 (2.01 for MeHg)
(4.34 for adults)
Schober et al. 2003 USA705 children aged 1-5 years
1709 adults aged 16-49 years
0.34
1.02
Seifert et al. 2000 German712 children aged 6-14 years
3958 adults aged 25-69 years
0.49
0.77
Batáriová et al. 2006 Czech333 children aged 8-10 years
1188 adults aged 18-58 years
0.42
0.89
• Mercury levels in children and adults in various regions
y = 0.8407x - 0.0676
R2 = 0.7813
0
1
2
3
4
5
6
7
8
1 2 3 4 5 6 7 8
[T-Hg] (ng/g)
[Me
Hg
] (n
g/g
)
2. Hg levels in Blood
• Mercury exposure study in children is of
interest because of continuing
neurobehavioral development during
this life stage.
• The difference between adults and
children may be due to differences in
toxicokinetics, dose frequency, body
size etc.
Correlations of T-Hg in sediment
y = 25.229x - 129.54R² = 0.2584
0
50
100
150
200
250
300
350
6 11 16 21
T-H
g(n
g/g
)
LOI(%)
T-Hg & LOI(%)
0
50
100
150
200
250
300
350
0.0 2.0 4.0 6.0
총수
은(n
g/g
)
Sulphur content(%)
T-Hg & Sulphur
y = 0.0124x - 0.0779R² = 0.6667
0
0.5
1
1.5
2
2.5
3
3.5
4
4.5
5
0 100 200 300 400
MeH
g(n
g/g
)
T-Hg(ng/g)
T-Hg & MeHg
0
50
100
150
200
250
300
350
0.00 0.10 0.20 0.30 0.40
T-H
g(n
g/g
)
Nitrogen Content(%)
T-Hg & T-N
3. Study of Lake An-dong
T-Hg in Soil
0.00
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
S-0(7km) S-1(20km) S-2(25km) S-3(50km)
T-H
g (
mg
/kg
)
Distances from the Hg source
2009.5 (Spring)
2009.10 (Fall)
3. Study of Lake An-dong
-100
-80
-60
-40
-20
0
0.000 0.050 0.100
cm
T-Hg(mg/kg)
Suk-po (Zinc smelter)
Jae-san
Ye-an
Chung-gi
Chun-yang
Distribution of Mercury and Methylmercury in Sediment, Freshwater fish and
human blood in South Korea
Young-Hee Kim, Sun-Kyung Shin, Sub-Jung Lee, Jin-Seok Han, Eun-Jin Hong, Gi-Taeg Jung Chemicals Behaviors Research Division, National Institute of Environmental Research, Incheon, Republic of Korea
According to UNEP’s Report in 2008, Republic of Korea is one of the largest
mercury emitting country with emission amount of 32 tones and recent studies showed
total mercury levels of blood in Korean were much higher than those in other countries
(investigated by Korea Ministry of Environment in 2005). Thus, there are growing
needs of ecosystem mercury monitoring to evaluate the effectiveness of mercury
emission controls by regulations. Among the mercury species, methylmercury has
been concerned as the most harmful mercury species due to its high toxicity, high
solubility in lipids, which increases the potential for biological uptake and
bio-concentration, and common occurrences in the environment.
The present works described the current status of total mercury and methylmercury
levels in freshwater fish and sediment from Korean peninsula. Total mercury
concentrations in the freshwater fish were in the range of 20.4 ~ 454 ng․g-1 (mean 175.1
ng․g-1 ) and methylmercury concentrations were in the range of 12.9 ~ 424 ng․g-1
(mean 143.2 ng․g-1 ). Total mercury and methylmercury concentrations in sediment
which were categorized plant effluent, urban stream, river, lake and reservoir were in
the range of 2.43~1,564.17 ng․g-1 and N.D.~5.95 ng․g-1, respectively.
Recently, the study for developing the mercury mass balance in Lake An-dong has
been started to identify possible mercury pollution sources in the lake. Mercury and
methylmercury were measured in atmospheric, tributary, open-lake water column,
sediment, planktons and fish samples in the catchments area. Lake An-dong, an
artificial freshwater lake is located on the upstream of River Nak-dong. The
possibilities of historical mercury pollution have been identified by the location of
more than 50 abandoned gold mines. The results of this study are thus expected to
offer valuable insights for the sources of mercury loading through the watershed.