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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.