NIMD Forum 2010 Distribution of Mercury and methylmercury ... · PDF fileDistribution of Mercury and methylmercury in South Korea ... Good Hg monitoring program is crucial: 1) ...

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)


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)


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


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.


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.


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)


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).


http://100.naver.com/100.nhn?type=image&media_id=256982&docid=5756&dir_id=0601220307

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)


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


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


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)

http://water.nier.go.kr/waterEasy/selectPicture.do?type=pictureDetail&seq=65&code=4

http://water.nier.go.kr/waterEasy/selectPicture.do?type=pictureDetail&seq=65&code=4

National Map for Average Estimated Fish tissue concentration

- Under construction !


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)


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


(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



(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


(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


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


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


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


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


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


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


• 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


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


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


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


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


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)


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


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


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


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


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


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


0.49

0.77

Batáriová et al. 2006 Czech333 children aged 8-10 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


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)


-100

-80

-60

-40

-20

0

0.000 0.050 0.100

cm

T-Hg(mg/kg)


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.

NIMD Forum 2010 Distribution of Mercury and methylmercury ... · PDF fileDistribution of Mercury and methylmercury in South Korea ... Good Hg monitoring program is crucial: 1) ...

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