National Institute for Agro-Environmental Sciences, Japan

National Institute for Agro-Environmental Sciences, Japan

Nobuyasu SEIKENobuyasu SEIKE

Temporal Trend of POPs Residue in Japanese Agricultural Soils

Temporal Trend of POPs Residue in Japanese Agricultural Soils

Agricultural soils (paddy and upland) periodically collected from all over Japan since 1960s are preserved in the National Institute for Agro-Environmental Sciences (NIAES).

Agricultural soils (paddy and upland) periodically collected from all over Japan since 1960s are preserved in the National Institute for Agro-Environmental Sciences (NIAES).

Air-dried and sieved (<2 mm) soils were preserved in polyethylene bottles at room temperature.

Air-dried and sieved (<2 mm) soils were preserved in polyethylene bottles at room temperature.

Preserved SoilsPreserved SoilsPreserved SoilsPreserved Soils

(15 sites)(15 sites)

Sampling SitesSampling Sites

Dioxins and Dioxin-like PCBsDioxins and Dioxin-like PCBs7 sites7 sites

Organochlorine PesticidesOrganochlorine Pesticides15 sites15 sites

● Temporal changes of dioxins and dioxin-like PCBs concentrations associated with their sources in paddy soils

● Temporal changes of dioxins and dioxin-like PCBs concentrations associated with their sources in paddy soils

TopicsTopicsTopicsTopics

● Temporal changes of organochlrine pesticides concentrations in paddy soils● Temporal changes of organochlrine pesticides concentrations in paddy soils

● In order to provide the factors for the decline of POPs in soils, half-lives for the disappearance of POPs in paddy soils were calculated.

● In order to provide the factors for the decline of POPs in soils, half-lives for the disappearance of POPs in paddy soils were calculated.

Dioxins (PCDD/Fs)Dioxins (PCDD/Fs)

(x + y = 1~ 8)(x + y = 1~ 8)(x + y = 1~ 8)(x + y = 1~ 8)

OCl xCl x Cl yCl y

O

OCl xCl x Cl yCl y

PCDDsPCDDs PCDFsPCDFs

Temporal Change of PCDD/Fs Conc. Temporal Change of PCDD/Fs Conc. in Japanese Paddy Soilsin Japanese Paddy Soils

Temporal Change of PCDD/Fs Conc. Temporal Change of PCDD/Fs Conc. in Japanese Paddy Soilsin Japanese Paddy Soils

0

100

200

300

400

500

Sampling YearSampling Year

Max.Max.

MeanMean

Min.Min.

*Ministry of *Ministry of Environment Environment and Ministry of and Ministry of Agriculture, Agriculture, Forestry, and Forestry, and Fisheries (2001)Fisheries (2001)

*Ministry of *Ministry of Environment Environment and Ministry of and Ministry of Agriculture, Agriculture, Forestry, and Forestry, and Fisheries (2001)Fisheries (2001)

pg-T

EQ

g-1-d

rypg

-TE

Q g

-1-d

ry

PCDD/Fs concentrations ware increased drastically during the 1960s, PCDD/Fs concentrations ware increased drastically during the 1960s,

began decreasing in the 1970s gradually. began decreasing in the 1970s gradually.

-

20,000

40,000

60,000

80,000

100,000

1955 1960 1965 1970 1975 1980 1985 1990 1995 2000

10

100

1,000

10,000

100,000

PC

DD

/Fs

Em

issi

on (

kg)

PC

DD

/Fs

Em

issi

on (

kg)

Con

cent

ratio

n (p

g g-1

)C

once

ntra

tion

(pg

g-1)

OCDD Conc.OCDD Conc.

1368/1379-TeCDD Conc.

1368/1379-TeCDD Conc.

YearYear

PCPPCPCNPCNP

Emission of PCDD/Fs, and Emission of PCDD/Fs, and OCDD 1,3,6,8-TeCDD Concentration OCDD 1,3,6,8-TeCDD Concentration

Emission of PCDD/Fs, and Emission of PCDD/Fs, and OCDD 1,3,6,8-TeCDD Concentration OCDD 1,3,6,8-TeCDD Concentration

Rapid increasing of PCDD/Fs concentrations are due to use of PCP and CNPRapid increasing of PCDD/Fs concentrations are due to use of PCP and CNP

PCA PlotPCA PlotPCA PlotPCA Plot

199919961993

19901987

1984

1981197819751972

1969

19661963

1960

Deposition(Combustion)

CNP

PCP

-0.4

-0.3

-0.2

-0.1

0

0.1

0.2

-0.4 -0.2 0 0.2 0.4 0.6 0.8

CNPCNP PCPPCPPC1 (86%)PC1 (86%)

PC

2 (1

2%)

PC

2 (1

2%)

PCDFsdominatePCDFsdominate

PCDDsdominatePCDDsdominate

Site 2Site 2

CombustionCombustion

Paddy SoilsPaddy Soils19601960 19661966 19721972 19991999

CNPCNPPCPPCP CombustionCombustion

Paddy SoilsPaddy Soils19601960 19661966 19721972 19991999

CNPCNPPCPPCPPCDD/Fs produced from combustion processes PCDD/Fs produced from combustion processes was thought to be the major source before PCP was thought to be the major source before PCP was usedwas used

The PCDD/F profiles in the paddy soils changed The PCDD/F profiles in the paddy soils changed significantly after using significantly after using PCPPCP and and CNPCNP in the in the 1960s and the 1970s 1960s and the 1970s

There were few significant changes in the There were few significant changes in the PCDD/Fs profiles. Namely, another important PCDD/Fs profiles. Namely, another important PCDD/Fs source have not existed since 1980s.PCDD/Fs source have not existed since 1980s.

Quantitative Source Identification by CMB*Quantitative Source Identification by CMB*Quantitative Source Identification by CMB*Quantitative Source Identification by CMB**developed by Kashiwagi (2002) J. Appl. Statist. *developed by Kashiwagi (2002) J. Appl. Statist.

~1960 (before PCP use): originated from combustion processes ~1960 (before PCP use): originated from combustion processes

early-1960s ~ mid-1960s: PCPearly-1960s ~ mid-1960s: PCP

0%

10%

20%

30%

40%

50%

60%

70%

80%

90%

100%

Con

trib

utio

n (%

)C

ontr

ibut

ion

(%)

PCPPCP CNPCNP

CombustionCombustion

0%

10%

20%

30%

40%

50%

60%

70%

80%

90%

100%

Con

trib

utio

n (%

)C

ontr

ibut

ion

(%)

PCPPCP CNPCNP

CombustionCombustion

end-1960s ~ : PCP and CNP (exceed 95%)end-1960s ~ : PCP and CNP (exceed 95%)

Mass Balance of PCDD/Fs in Japanese Mass Balance of PCDD/Fs in Japanese Paddy Fields (1958-2000) Paddy Fields (1958-2000)

Mass Balance of PCDD/Fs in Japanese Mass Balance of PCDD/Fs in Japanese Paddy Fields (1958-2000) Paddy Fields (1958-2000)

-

200,000

400,000

600,000

800,000

1,000,000

1960 1965 1970 1975 1980 1985 1990 1995 2000

ResidueResidue

RunoffRunoff

UnknownUnknown

Curtailment of Paddy Fields

Curtailment of Paddy Fields

YearYear

PC

DD

/Fs

(kg)

PC

DD

/Fs

(kg)

CumulativeInput

CumulativeInput

Disappearance from Paddy Field

Disappearance from Paddy Field

Half-lives: 17.6 yr Half-lives: 17.6 yr *Runoff : 2% / yr　*Runoff : 2% / yr　 *Masunaga et al. ES&T (2001)

*Ministry of *Ministry of Environment Environment and Ministry of and Ministry of Agriculture, Agriculture, Forestry, and Forestry, and FisheriesFisheries

*Ministry of *Ministry of Environment Environment and Ministry of and Ministry of Agriculture, Agriculture, Forestry, and Forestry, and FisheriesFisheries

Nationwide Survey*

Nationwide Survey*（ 1999-2002）（ 1999-2002）

Dioxin-Like PCBsDioxin-Like PCBsnon-ortho PCBsnon-ortho PCBsmono-ortho PCBsmono-ortho PCBs

12 CongenersKnown major source

- Commercial PCBs (Kanechlors)

- Combustion Processes

50 ×106 kg50 ×106 kgTotal PCBs use in JapanTotal PCBs use in Japan

banned at 1974banned at 1974

0

0.5

1

1.5

YearYear

pg-T

EQ

g-1-d

rypg

-TE

Q g

-1-d

ry

Max.Max.

MeanMean

Min.Min.

Temporal Trend of Dioxin-like PCBsTemporal Trend of Dioxin-like PCBs Concentrations in Paddy Soils Concentrations in Paddy Soils

Temporal Trend of Dioxin-like PCBsTemporal Trend of Dioxin-like PCBs Concentrations in Paddy Soils Concentrations in Paddy Soils

Dioxin-like PCBs concentrations were considerably lower than PCDD/Fs.Dioxin-like PCBs concentrations were considerably lower than PCDD/Fs.

YearYear

pg-T

EQ

g-1-d

rypg

-TE

Q g

-1-d

ry

0.1

1

10

100

1000PCDD/Fs

Dioxin-like PCBs

Dioxin-like PCBs concentrations are decreased during 1970s, and then, began to increasing gradually.Dioxin-like PCBs concentrations are decreased during 1970s, and then, began to increasing gradually.

The ratio of #126 to ΣΣPentaCBsPentaCBs have been increased since 1970sThe ratio of #126 to ΣΣPentaCBsPentaCBs have been increased since 1970s

The Ratio of #126 to The Ratio of #126 to ΣΣPentaCBsPentaCBsThe Ratio of #126 to The Ratio of #126 to ΣΣPentaCBsPentaCBs

= Dioxin-like PCBs originated from combustion processes have been increasing gradually= Dioxin-like PCBs originated from combustion processes have been increasing gradually

0.0%

1.0%

2.0%

3.0%

4.0%

5.0%

YearYear

Rat

io o

f #1

26

Rat

io o

f #1

26

KanechlorKanechlor

CombustionCombustion

0.44%0.44%

56%56%～～

（#126 / Σ PentaCBs）（#126 / Σ PentaCBs）6 congeners (#105, #114, #118, #123, #126)

Organochlorine Pesticides (OCPs)Organochlorine Pesticides (OCPs)

AldrinAldrin 2.5×102.5×1066 kg kg

DieldrinDieldrin 0.7×100.7×1066 kg kg

EndrinEndrin 1.5×101.5×1066 kg kg

ChlordanesChlordanes 0.2×100.2×1066 kg kg

17 ×1017 ×1066 kg kg for domestic pest controlfor domestic pest control

DDTsDDTs 23 ×1023 ×1066 kg kg

HCHsHCHs 280 ×10280 ×1066 kg kg

HeptachlorsHeptachlors 1.5×101.5×1066 kg kg

HCBHCB Not RegisteredNot Registered

MirexMirex Not RegisteredNot Registered

Usage in Japan (A.I base)Usage in Japan (A.I base)CompoundsCompounds Banned YearBanned Year

19711971

19711971

19751975

19751975

19751975

19751975

19681968

19861986

0.001

0.01

0.1

1

10

100

1000

1960 1965 1970 1975 1980 1985 1990 1995 2000 2005

ngg-

1-d

ryng

g-1-d

ry

YearYear

0.001

0.01

0.1

1

10

100

1000

1960 1965 1970 1975 1980 1985 1990 1995 2000 2005

ngg-

1-d

ryng

g-1-d

ry

YearYear

DDTsDDTs

HCHsHCHs

DrinsDrins

ChlordanesChlordanes

HCBHCBHPCLsHPCLs

MirexMirex

Temporal Change of OCPs Conc. Temporal Change of OCPs Conc. in Japanese Paddy Soilsin Japanese Paddy Soils

Temporal Change of OCPs Conc. Temporal Change of OCPs Conc. in Japanese Paddy Soilsin Japanese Paddy Soils

Temporal changes in OCPs concentrations in paddy soils reflected the use of pesticides. Temporal changes in OCPs concentrations in paddy soils reflected the use of pesticides.

Temporal Change of OCs Conc. in Human Temporal Change of OCs Conc. in Human Breast Milk from Osaka, JapanBreast Milk from Osaka, Japan

Temporal Change of OCs Conc. in Human Temporal Change of OCs Conc. in Human Breast Milk from Osaka, JapanBreast Milk from Osaka, Japan

0.01

0.1

1

10

100

1970 1975 1980 1985 1990 1995 2000

β-HCH

DDE

DDT

Dieldrin

CHL

PCB

μgg-

1-f

atμg

g-1-f

at

Sampling YearSampling Year

Konishi et al. Arrch. Environ. Contam. Toxicol. (2001) Konishi et al. Arrch. Environ. Contam. Toxicol. (2001)

Half-lives in Paddy SoilsHalf-lives in Paddy SoilsHalf-lives in Paddy SoilsHalf-lives in Paddy SoilsC(x)= C(x0)exp(-k(x)t)C(x)= C(x0)exp(-k(x)t) C(x0)：Original Conc.C(x0)：Original Conc.

C(x)：Final Conc.C(x)：Final Conc.

t：yearst：years

K(x)：Loss rate constantK(x)：Loss rate constant

0 5 10 15 20 25

α-HCH

β-HCH

γ-HCH

Dieldrin

p,p'-DDT

p,p'-DDD

p,p'-DDE

PCDD/Fs

(Mean ±S.D.)(Mean ±S.D.)

Half-lives (Years)Half-lives (Years)

Kow vs Half-livesKow vs Half-livesKow vs Half-livesKow vs Half-lives

1368D1379D

12378D

123478D

123678D 1234678D

OCDD2378F

123478F

234678F1234678F

OCDF

β-HCH

p,p'-DDE

Dieldrin

α-HCHγ-HCH

p,p'-DDD

p,p'-DDT

0

5

10

15

20

25

30

3 4 5 6 7 8 9 10

Log KowLog Kow

Y=3.5X-8.8Y=3.5X-8.8r=0.61, p<0.01r=0.61, p<0.01

PCDD/FsPCDD/Fs

OCPsOCPs

Hal

f-liv

es(y

ears

)H

alf-

lives

(yea

rs)

Correlations between Half-lives and Correlations between Half-lives and Correlations between Half-lives and Correlations between Half-lives and (H

alf-

life

Yea

r)(H

alf-

life

Yea

r)

Carbon content (%)Carbon content (%)

0

5

10

15

20

25

30

5 10 15 20

β-HCH

p,p'-DDE

0

5

10

15

20

25

30

0 2 4 6 8 10

β-HCH

p,p'-DDE

Carbon Content Annual Mean Temp.

Annual Mean Temp (℃)Annual Mean Temp (℃)

p,p’-DDEr =0.81（p < 0.01）

β-HCHr =0.56（p < 0.05）

β-HCHr =-0.24（p = 0.39）

p,p’-DDEr =-0.43（p = 0.11）

Concluding RemarksConcluding Remarks

It is, therefore, expected that further POPs contamination on agricultural soil will not occur, and POPs concentrations in agricultural soil as well as air, water and biota, will decrease gradually.

It is, therefore, expected that further POPs contamination on agricultural soil will not occur, and POPs concentrations in agricultural soil as well as air, water and biota, will decrease gradually.

● In Japan, use of OCPs was already banned in the early 1970s. ● In Japan, use of OCPs was already banned in the early 1970s.

● PCP and CNP was also banned in the 1990s. ● PCP and CNP was also banned in the 1990s.

● The content of PCDD/Fs is checked at the agricultural chemicals registration ● The content of PCDD/Fs is checked at the agricultural chemicals registration

● The emission gas controls on waste incinerators and improvements of incineration facilities have been imposed since end of 1990s by the Japanese government

AcknowledgmentsAcknowledgments

This work was supported in part by a Grant-in-aid (Hazardous Chemicals and Environmental Research) from the Ministry of Agriculture, Forestry and Fisheries and the Ministry of Environment, Japan, respectively.

This work was supported in part by a Grant-in-aid (Hazardous Chemicals and Environmental Research) from the Ministry of Agriculture, Forestry and Fisheries and the Ministry of Environment, Japan, respectively.

I thank Dr Otani, T. and Dr Eun, H. National Institute for Agro-Environmental Sciences, for useful discussions. I thank Dr Otani, T. and Dr Eun, H. National Institute for Agro-Environmental Sciences, for useful discussions.