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Carbon Sequestration in Soil for long term -From formation of melanic Andosols and its

application-

Takeshi Suzuki27th April 2009

contentscontents 1.background2. Formation of melanic Andosol(experimental pedology)3.Application for this technique for3.Application for this technique for agriculture

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Atompsphere 730（Annual increase 3）

Soil as carbon reserves (carbon distribution)（GtC）

（Annual increase 3）

Terrestrial animals 560Soil 1200（area 130×109ha）（ ）

Surface water 2800Sea animals 3

Mid-deep water 3500marine sediment 24800000

（角皆 1989）

Terrestrial carbon reserves (climate & land use)

1.9%

1.7%

1.3% 3.2%

Tropical forests

Temperate forests

45.5%

18.9%

14.2%

0.6%

carbon stocks of plant466PgC

11.3%

5.2%

24.6%10.0%

6.3%

6.7%

11.8%

carbon stocks of soil2011PgC

p

Boreal forests

Tropical savannas &grasslandsTemperate grasslan& shrublandsDeserts and semi desertsTundra

12.7% 8.6%15.4%

Tundra

Croplands

Wetlands

Climate Change 2003 (IPCC)Organic soil(Unstable)

focus

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Terrestrial carbon concentration (climate & land use)

80

C m

-2) plant

soil

Organic soil(Unstable)

20

40

60

arbo

n C

once

ntra

tion

(kg

0Tropical

forests

Temperate

forests

Boreal

forests

Tropical

savannas &

grasslands

Temperate

grasslands &

shrublands

Deserts and

semi deserts

Tundra Croplands Wetlands

Ca

Climate Change 2003 (IPCC)Andosols, Mollisols

What is Andosols

Andosols cover more than0.8 percent of the earth’ssurface (Soil survey staffof USDA 1999). The

l fcentral concept of anAndosol is that of a soildeveloping in volcanicejecta and/or involcaniclastic materials,the colloidal fraction ofwhich is dominated byshor-range-order mineralsor Al-humus complexor Al-humus complex.

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Soil age from 14C

14C age Andosols

14C age （year B P）

Cambisols Plinthosols Regosols Podzols Andosols

Virgin soil（incl. buried soils）

Cropland （surface soil）

14C age （year B.P.）

200～28,000（ Kumada 1987）

460～3,820（Yamada 1984）

Giant soil profile in Kagoshima pref. of Japan

1914

BC5,300

BC6,700

BC11,000～14,000

2m

BC23,000

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Type of Humic acid of melanic Andosols

Type AType A120

160Typical humic acid inAndosols and Mollisols

Historical method

Type AType A

RpP

B

0

40

80

120

RF

The melanic horizon is a thick, black horizon at ornear the surface, which is typically associatedwith short-range-order minerals (commonlyallophane) or with organo-aluminium complexes.It has a low bulk density and contains highly

Andosols which have melanic epipedon

0.9 0.7 0.5 0.30

ΔlogK

ΔlogK=logA400-logA600The melanic index is used for soil classification

humified organic matter that shows a lower ratioof fulvic acids to humic acids compared with thefulvic horizon (WRB 2006).

MI=A450/A520RF=16*A600/C (of extracted solution)C:carbon contents of solution(mg/L)

How to form melanic Andosols

Hypothesis 1Active metals like Al and Fe,supplied from weathered

Hypothesis 2Cultivated Japanese pampasgrasses (Miscanthus sinensisA ) and its charred materialsvolcanic materials, catalize

and stabilize humic acidsthrough complexationreactions

A.) and its charred materialsare the major carbon source ofhumic acids

charred materials

AlFe

Mn

Melanichumus

Melanichumus

??Fe

It’s takes 200 years to clear the hypothesis in natural condition

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Thermal incubation method for hypothesis 1

Plant residues + fresh volcanic ash + daily water at 90℃ or 75℃

(Otsuka et al 1994)From thermochemical kinetics, it corresponding to natural condition.(It will take 200 years for formation melanic HA)

contentscontents 1.background2. Formation of melanic Andosol(experimental pedology)3.Application for this technique for3.Application for this technique for agriculture

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Objective of this study

1.Comparing chemical structural chracteristic between humicacid (HA) of natural Andosols and humic acid like substance

Using thermal incubation method

acid (HA) of natural Andosols and humic acid like substance(HALS) of artificial Andosols (volcanic ash + plant residues)by NMR, IR, HPSEC etc.

2.Cralify the relationship between HALS of artificialAndosols (volcanic ash + plant residues) and extractablemineralmineral

3.Create melanic Andosols from purchasable mineral andplant residues

How to make How to make melanicmelanic humushumus

Organic wastesOrganic wastes

Wood shavings (broadleaf)Rice straw

Volcanic ash

Waste : volcanic ash=1:4(w/w)

Wood shavings(conifer)

90℃, daily water

Claryfiy chemical structure of humic acid

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Change of colore

0 5025 75 100 160120

Rice straw＋volcanic ash

0 5025 75 100 160

Broadleaf wood shavings

+ volcanic ash

Conifer wood shavings

+

0 5025 75 100 160

+ volcanic ash

Last samples contained melanic humus

80

100

80

100

80

100

Type of Humic acid

160daysA A A

0

20

40

60

0.30.81.31.8

ΔlogK

RF

0

20

40

60

0.30.81.31.8

ΔlogK

RF

0

20

40

60

0.30.81.31.8

ΔlogK

RF

0days 0days 0days

160days160days

PRp

B

P Rp

B

PRp

B

Rice straw ConiferBroad leaf

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IRスペクトル

0day

Shimadzu FT-IR8300KBr method

2920cm-1

Aliphatic C-H1560cm-1

N-H、C=N

1600cm-1

Aromatic C=H1720cm-1

C=O

0day

25days

50days

100days

4000 3000 2000 1000 50015004000 3000 2000 1000 5001500 （cm-1） （cm-1） 4000 3000 2000 1000 5001500 （cm-1）

Rice straw CanopyBroadleaf

1H-NMR spectra of HALS7.26.5

HOD3.7 1.6 1.2 0.9 Increase Alphatic H

of α−position Bruker DPX250observation frequency:250.1315MHz:Pulse width 30°Time delay：2 5sec

Rice straw 0day

Canopy 0day

Canopy 100days

M h l H

Decrease Alphatic HOf β−position

Decrease Alphatic HOf γ−position

Time delay：2.5secNumber of scan：200Internal standard：HDO（4.7ppm）

Rice straw 100days

H H

α

Broadleaf 0day

Broadleaf 100days

12 10 8 6 4 2 0

chemical shift (ppm)

Aromatic Hincrease

Methoxyl HH2C

CH2

H2C

CH2

CH3

β γ

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13C-NMR spectra of natural HA

扇 山

TM

S

305674120

130

150

175

猪 頭猪之頭

Bruker AM 250InvGate Medtd.BB 10 mm probePW: 45゜RT: 2.5sNS: 20 000

OCH3

猪 頭

菅 平

長 峰

鉢 伏

ｳ ｧ ｶ ｳ

Ａ

型

腐

植

酸

猪之頭 NS: 20,000Solv: NaOH-D2O

Type A HA

N T A HA

High aromaticity

C h e m i c a l s h if t ( p p m )

花 折

ﾘ ｸ ﾞ ﾆ ﾝlignin

No Type A HA

-COOHCarbo-hydrate

aliphaticOH

13C-NMR spectra of HALS of artificial Andosols

Aliphatic→ decrease

Methoxyl groupRice straw 0day

TMS

30

56

74105

120

130

150

175

194

OCH3

Carboxyl group→ increase

Carbonyl group

phenol→ broad signal

aromaticity

Bruker AM 250InvGate Medtd.

50days

100days

160 days

25days

BB 10 mm probePW: 45゜RT: 2.5sNS: 20,000Solv: NaOH-D2O

Chemical shift (ppm)

Broadleaf0day

160 days

-COOH Carbo-hydrate

aliphaticOH

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Conclusion from 13C-NMRspectra

194 175 150 130120105 TMS305674

decrease

Rice straw ０day

Rice straw 160days

Carbohydrate of C1

Phenolic

Aromatic CH

Natural Tpe A HA-CH2--OMe

Carbohydrate y 1

COOHC=O

decreaseincrease

（ppm）

Change of average molecular weight by HPSECsample:0.16% 10μLcolumn：G6000PWXL ×２（300×8mm tohsohFlow rate：0.6mL min-1

detect：UV-VIS（400nm)

strong Ri CanopyBroadleafstrongshape Rice straw CanopyBroadleaf

shape Intensity of ABS

weakbroad

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Change of average molecular weight by HPSEC

120000

140000

Rice strawcanopyBroadleaf

0

20000

40000

60000

80000

100000

0 20 40 60 80 100 120

重量

平均

分子

量

Natural Atype HA29,554

培養日数（日）

Correlation of RF value and extractable mineral

Incubated sample were extracted by Na-Dithionite –Citrate-Bicarbonate (DCB)Acid o alic acid (TAMM) 100

120

Rice straw:r = 0.845***

Broadleaf:r = 0.881***

Mineral Carbon SourceExtracted Rice straw Broadleaf conifer

Fed 0.798*** 0.719** 0.399*

Feo 0.782*** 0.646** 0.379*

Acid oxalic acid (TAMM)Sodium Pyrophosphate (NaPP)

20

40

60

80

100

RF

conifer:r = 0.580*

oFep 0.550* 0.857*** 0.552*

Ald 0.852*** 0.797*** 0.576*

Alo 0.845*** 0.881*** 0.580*

Alp 0.660** 0.778*** 0.673**

0

0 10 20 30 40

Alo extracted (mmol kg‐1)

RS BL PT

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Which minerals make Which minerals make melanicmelanic humushumus

Organic wastesOrganic wastes

Wood shavings (broadleaf)Rice straw

minerals

plant : volcanic ash=1:4(w/w)

Wood shavings(conifer)

Al2(SO4)3,Al(OH)3,Al2O3

M SO M O

FeSO4,FeOOH,Fe2O3

90℃, daily water

Clarify type of humic acid

MnSO4,MnO2

Type of HALS

140

160

180

200b

A140 

160 

180 

200 c

A140

160

180

200a

180days180days

180d

0

20

40

60

80

100

120

0.3 0.5 0.7 0.9 1.1 1.3 

RF

Δ log K

B

Rp

P

0 

20 

40 

60 

80 

100 

120 

0.3 0.5 0.7 0.9 1.1 1.3 

RF

Δ log K

B

Rp

P

0

20

40

60

80

100

120

0.3 0.5 0.7 0.9 1.1 1.3 

RF

Δ log K

A

B

Rp

P

180days

0day 0day 0day

Type of HA formed from the three compounds.a: Al2(SO4)3; b: FeO(OH);c: MnO2*The line order of connection was for length ofincubation period from 0 day to 180 days.

Rice strawBroadleafconifer

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Change of Plant Residue to HALS

Type of HAAliphatic chain-CH-、NH-

aromaticityC=C -COOH

Molecular weight

Molecular weight distribution

0day Rp COOH

COOH

HOOC

100days A

COOH

HOOC

COOH

COOH

Close to natural Type A humic acid

hypothesis

Plant residues

Volcanic ejecta(with inactive Fe, Al, Mn, Si,)

Mixing

Biotic transformationAbiotic weathering

Weathering volcanic ejecta(TAMM soluble active metal, FeO(OH), MnO2)

Type Rp HA

Catalytic effectpromotes Type A HA formation

Abiotic

Mainly

Ma

Type A HA

Weathering in low pH condition

Weathering volcanic ejecta(with DCB, TAMM soluble active metal Al)

Complex with humusStabilizes Type A HA

2:1 layer clay mineral(smectite )

Mechanismis unclear

Increase carboxyl groupMake low pH condition

aillardR

eaction?

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contentscontents 1.background2. Formation of melanic Andosol(experimental pedology)3.Application of this technique for3.Application of this technique for agriculture

Normal humuscompost

CO2Objective of this studyObjective of this study

compost application

Organic wastes

With volcanic ash

Quick cycle of CUsual way Contribution to

decrease greenhouse gas

施用

Melanic humuscompost

Long term Carbon Sequestration in soil

compost application

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Increase of coal demand

Coal Information 2004(IEA)

Ce: coal equivalent•Alternative energy of oil•Advanced technology for combustion of coal• Coal reserve will not finish after 100 years

Characteristic of coal fly ash and volcanic ash

compositioncomposition（％）（％）SiOSiO22 4040～～7575AlAl22OO33 1515～～3535

Coal fly ash (CFA)

FeFe22OO33 22～～2020CaOCaO 11～～1010

pH: more than10pH: more than10

compositioncomposition（％）（％）SiOSiO about 60about 60

Volcanic ash (From Mt. Sakurajima, acid rock)

SiOSiO22 about 60about 60AlAl22OO33 1212～～1515

FeFe22OO33 66～～99CaOCaO 55～～77

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How to make How to make melanicmelanic humus from CFAhumus from CFA

Rice straw

Coal fly ash

Waste : Coal fly ash=1:4(w/w)

H dj d 490℃, daily water

Clarify type of HA

pH adjusted to 4

Type of Humic acid

pH adjusted CFA

CFA160daysA

120

140

Volcanic Ash

Rp

B

P40

60

80

100

RF

0day

Rp

0

20

0.500.700.901.10

ΔlogK

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Large Large scalscal creation of creation of melanicmelanic AndosolsAndosols

Ri tBroadleaf sawdust

W d hiRice straw

CFAMaterial:CFA=1:4(w/w)

WoodchipBroadleaf bark

Daily water addition 110℃ for 120

HALS characterization

Adjust pH4 by H2SO4

Commercially suppliedMachine for food scraps(National, MS-N11)

Change of colore

Rice straw

W d hi

Broadleaf saw dustWood chip

0 30 60 90 120

Broadleaf bark0 30 60 90 120

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Type of HA

120days120

140

A

Rice straw

Broadleaf sawdust

Wood chip

Broadleaf sawdust0day40

60

80

100

RF

Rp

B

0day0day 0day

0

20

0.4000.6000.8001.0001.2001.4001.6001.800

ΔlogK

Rp

1313C C NMR spectra of NMR spectra of HALfromHALfrom natural and artificial natural and artificial AndosolsAndosols

SD-A-300d

WC-A-300d

WC-B-90d

TMS

TMS

From 13C NMR spectra, chemical

RS-B-90d

RS-B-120d

WC-B-120d

BK-B-120d

bA

p ,structure (carbon skeleton) is very similar

SD-B-90d

SD-B-120d

100 0ppm200

A

M

100 0ppm200

Humic acid from natural melanic Andosols

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Measurement from integral of 13CMeasurement from integral of 13C--NMRNMR

Ali-C

2

4

6

8

10

mm

ol g

-1 S

bA

AM Car-C

2

4

6

8

10

mm

ol g

-1

S

bA

A

M

Aromaticity1.5

0

COO-C15

Aro-C

0

10

20

30

40

mm

ol g

-1

S

bA

A M

0A

Phe-C**

0

2

4

6

8

10

mm

ol g

-1

S

bA A

M

Artificial HALS is higher amount of Phenolic carbon

0.0

0.5

1.0

mm

ol g

-1

S bA AM

0

5

10

mm

ol g

-1

S bAA

M

**significant difference P<0.01 Whitney-Mann U-test

×S: artificial HALS(N = 11)；◆ bA: buried Andosols (N = 3)；

◇ A: surface Andosols (N = 9) ；▲ M: Molisols (N = 3)；-average

Elemental compositionElemental composition Total carbon

20

40

60

atom

%

Total hydrogen

20

30

40

atom

%

0

20S bA A M

Total nitrogen

2

4

6

atom

%

S bA A M

Total oxygen**

20

30

atom

%

0

10 S bA A M

0 10

S bA A M

**significant difference P<0.01 Whitney-Mann U-test

×S: artificial HALS(N = 11)；◆ bA: buried Andosols (N = 3)；

◇ A: surface Andosols (N = 9) ；▲ M: Molisols (N = 3)；-average

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H/CH/C--O/C diagram form elemental compositionO/C diagram form elemental composition

2

0.5

1

1.5

H/C

otherbAAMS

-CO2

CH

00 0.2 0.4 0.6 0.8

O/C

-H2O -CH4

S: artificial HALS(N = 11)； bA: buried Andosols (N = 3)；

A: surface Andosols (N = 9) ； M: Molisols (N = 3)；-average

functional group analysis functional group analysis

468

1012

mm

ol g

-1

SbA A

34567

mm

ol g

-1

SbA

A M

-COOHTotal acidity**

02

m bA AM

012m

3

4

5

6

mol

g-1

SbA

A

M

Ar-OH**

0

1

2mm S M

**significant difference P<0.01 Whitney-Mann U-test

×S: artificial HALS(N = 11)；◆ bA: buried Andosols (N = 3)；

◇ A: surface Andosols (N = 9) ；▲ M: Molisols (N = 3)；-average

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HPSECHPSEC

15

20

a

2

3Mn** Mw

0

5

10

kDa

S bA A M

15

0

1

kDa

S bA A M

Mw/Mn×S: artificial HALS(N = 11)；

◆ bA: buried Andosols (N = 3)；

0

5

10

S bA A M**significant difference P<0.01 Whitney-Mann U-test

◆ bA: buried Andosols (N 3)；

◇ A: surface Andosols (N = 9) ；

▲ M: Molisols (N = 3)；

-average

Principal component analysisPrincipal component analysis

Variable：Aromacity （13C NMR)、N/C（elemental analysis）、carboxyl group、Phenolic hydoxyl group、Mn、Mw/Mn (HPSCEC)

Statistical value

(HPSCEC)method：correlation matrix

component1 component 2 component 3

Aromaticity (NMR) -0.520 0.019 0.419N/C 0.404 0.441 -0.308Carboxyl group -0.373 0.437 0.384Phenolic group -0.341 -0.525 -0.268Mn 0.267 -0.579 0.243Mw/Mn 0.490 -0.060 0.671Eigen value 2.948 1.830 0.470寄与率 0.491 0.305 0.078Cumulative proporsion 0.491 0.796 0.875

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Principal component analysisPrincipal component analysis

N/C

-COOH

Humic acid from natural melanic Andosols

Aromaticity

Humic acid from natural soil without Andosols

-OH Mn

Humic acid from artificial Andosols

If N content is increase and phenolic OH is decreased in HA from artificial Andosols, it would be same as natural melanic Andosols

Artificial Natural soil

Microbeactivity

Decomposed plant residue

Discussion and future researchDiscussion and future research

Fresh plant residueFew nitrogen

×ThermalMineral Microbe

activity

Melanic AndosolsHALS

OH

HOOC

×

Melanic Andosols

HA

OHHOOC

Fresh plant residue ＋

Nitrogen source

Decomposed plant residueThermal incubation?

Thermal incubation?

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Future researchFuture research

Decomposable activity in soil

Effect of soil amendment

CO

Microbial activity?

Property of fertilizer

Effect to plant

CO2

?Soil physical property ?

Soil chemical property?

Life Cycle Assessment (LCA)

p y

ash ? T-N ?

C/N ?pH ?

T-C ?

Danke schön

ありがとうございました

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ススキ草地からアカマツ林へススキ草地からアカマツ林へ

SGSG--GGgrassland

SGSG--FF

Forest after 40 years from grassland

Agricultural andosols

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insi

ty

0 30