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544

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547

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548

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549

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550

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551

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554

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555

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556

26.

23

557

Figure captions

558

Fig. 1. Location of sampling site illustrated on isopach map of To-Cu and To-Nb

559

tephras based on Machida and Arai (2003) (a) and sampling position in the soil

560

profile (b). To-a: Towada-a, To-b: Towada-b, To-Cu: Towada-Chuseri, To-Nb:

561

Towada-Nambu. The deposition ages of To-a* and To-b** are calculated 14C ages and

562

cited from Machida et al. (1981) and Oike and Shoji (1974), respectively. The

563

deposition ages of To-Cu*** and To-Nb*** are non-calculated 14C ages and cited from

564

Hayakawa (1983;1985).

565

566

Fig. 2. Relationship between δ13C and δ15N values of humin, humic acid (HA),

567

hydrophilic fulvic acid (FA1 and FA2), and hydrophobic fulvic acid (FA3 and FAIHSS)

568

fractions prepared from eight sub-horizon samples from a buried humic horizon

569

occurred between 147 and 187 cm depth of an Andosol near Towada volcano.

570

The δ13C and δ15N values of FA2 (152 - 157 cm and 162 - 167 cm depths) and FAIHSS

571

(172 - 177 cm depth) were not detected due to low yield.

572

573

Fig. 3. Solid-state cross polarization magic angle spinning 13C nuclear magnetic

574

resonance spectra of hydrophilic fulvic acid (FA1 and FA2), hydrophobic fulvic acid

575

(FA3 and FAIHSS), and humic acid (HA) fractions prepared from a sub-horizon sample

576

between 162 and 167 cm depth from a buried humic horizon occurred between 147

577

and 187 cm depth of an Andosol near Towada volcano.

578

579

Fig. 4. Comparison between deposition age of sub-horizon (●: Inoue et al., 2011) and

580

14

C age (○) of (a) humin, (b) humic acid (HA), (c and d) hydrophilic fulvic acid (c:

24

581

FA1, d: FA2), and (e and f) hydrophobic fulvic acid (e: FA3, f: FAIHSS) fractions

582

prepared from eight sub-horizon samples from a buried humic horizon occurred

583

between 147 and 187 cm depth of an Andosol near Towada volcano. Error bars

584

indicate the uncertainty (2σ) of the corresponding 14C age determination. The 14C age

585

of FA2 from the 2nd and 4th sub-horizons (152 - 157 cm and 162 - 167 cm depths)

586

and FAIHSS from the 6th sub-horizon (172 - 177 cm depth) was not detected due to

587

low yield.

25

(a)

(b)

Depth (cm)

To-a

AD 915*

To-b

2.2**

100

To-Cu

5.39 kyr BP***

Depth (cm) Sample code

-147

-152

8-1

-157

-162

-167

-172

200

8-2

8-3

8-4

8-5

To-Nb

8.37 kyr BP***

-177

8-6

-182

8-7

-187

8-8

300

humic horizon

Fig.1. Wijesinghe et al., 2019

tephras (pumice)

14

Humin

Humin

12

HA

HA

FA1

FA1

δ15N (‰)

10

FA2

FA2

FA3

FA3

FAIHSS

FAIHSS

y = 1.6038x+35.412

R = 0.5053

-25

-24

-23

-22

δ13C (‰)

Fig. 2. Wijesinghe et al., 2019

-21

-20

FA1

FA2

FA3

FAIHSS

HA

250

200

150

100

Chemical shift (ppm)

Fig. 3. Wijesinghe et al., 2019

50

50

142

147

152

157

162

167

172

177

182

(a) humin

(b) HA

y = 0.0313x - 26.678

R² = 0.9635

y = 0.0302x - 15.221

R² = 0.8359

187

142

147

Depth of soil profile (cm)

152

157

162

167

172

177

182

(c) FA1

(d) FA2

y = 0.0369x - 41.986

R² = 0.6596

y = 0.0287x + 13.243

R² = 0.9444

187

142

147

152

157

162

167

172

177

182

(e) FA3

y = 0.039x - 46.814

R² = 0.9182

187

4000

5000

(f) FAIHSS

y = 0.0333x - 28.873

R² = 0.7266

7000 4000

6000

14

Fig. 4. Wijesinghe et al., 2019

C age (yr BP)

5000

6000

7000

Table 1. Averaged C and N recovery of humin, humic acid (HA), hydrophilic fulvic acid (FA1

and FA2), and hydrophobic fulvic acid (FA3 and FAIHSS) fractions prepared from eight subhorizon samples from a buried humic horizon occurred between 147 and 187 cm depth of an

Andosol near Towada volcano.

SOC fraction

Humin

HA

FA1

FA2

FA3

FAIHSS

mean ± SD

C recovery (%)

85.4 ± 11.1

4.9 ± 1.2

5.7 ± 0.8

1.1 ± 1.1

1.9 ± 0.8

3.7 ± 2.0

102.7 ± 8.8

N recovery (%)

74.1 ± 7.2

3.3 ± 1.2

5.6 ± 0.9

1.3 ± 1.3

2.3 ± 1.5

2.0 ± 1.5

88.5 ± 5.9

Table 2. Averaged δ13C and δ15N values of humin, humic acid (HA), hydrophilic fulvic acid

(FA1 and FA2), and hydrophobic fulvic acid (FA3 and FAIHSS) fractions prepared from eight

sub-horizon samples* from a buried humic horizon occurred between 147 and 187 cm depth of

an Andosol near Towada volcano.

SOC fraction

δ13C‰

δ15N‰

humin

-22.1 ± 0.3

5.0 ± 0.4

HA

-23.9 ± 0.4

3.1 ± 0.5

FA1

-21.0 ± 0.5

7.7 ± 1.8

FA2

-21.3 ± 0.6

6.1 ± 1.0

FA3

-22.9 ± 0.5

5.6 ± 2.7

FAIHSS

-23.4 ± 0.4

5.2 ± 0.7

: The δ13C and δ15N values of FA2 (152 - 157 cm and 162 - 167 cm depths) and FAIHSS (172 177 cm depth) were not detected due to low yield.

Table 3. The C/N ratio of humin, humic acid (HA), hydrophilic fulvic acid (FA1 and FA2), and

hydrophobic fulvic acid (FA3 and FAIHSS) fractions prepared from eight sub-horizon samples

from a buried humic horizon occurred between 147 and 187 cm depth of an Andosol near

Towada volcano.

Sample

code

Sampling

C/N

depth

humin

HA

FA1

FA2

FA3

FAIHSS

(cm)

8-1

147-152

14.3

18.9

12.8

9.4

10.1

13.9

8-2

152-157

16.4

18.9

13.6

12.4

14.9

8-3

157-162

14.4

18.0

9.0

13.5

14.7

12.0

13.3

15.7

8-4

162-167

14.7

18.2

13.1

8-5

167-172

15.0

17.2

13.3

10.2

13.9

16.2

8-6

172-177

14.9

17.4

14.4

9.4

14.6

-*

8-7

177-182

14.5

17.5

13.7

10.0

14.4

16.7

8-8

182-187

14.7

17.7

11.7

12.6

14.4

17.4

mean ± SD

14.9 ± 0.7

18.0 ± 0.6

13.1 ± 0.9

10.1 ± 1.3

13.3 ± 1.5 15.7 ± 1.2

-*: The C/N ratio of FA2 (152 - 157 cm and 162 - 167 cm depths) and FAIHSS (172 - 177 cm

depth) was not detected due to low yield.

Table 4. Distribution of carbon species and aromaticity values of humin, humic acid (HA), hydrophilic fulvic acid (FA1 and

FA2), and hydrophobic fulvic acid (FA3 and FAIHSS) fractions prepared from four sub-horizon samples (147 - 152, 162 - 167,

172 - 177, and 182 - 187 cm depths) from a buried humic horizon occurred between 147 and 187 cm depth of an Andosol near

Towada volcano.

Fine fractionated

organic C

Aromaticitya

C species (%)

Carboxyl C

(165 - 190 ppm)

Aromatic C

(110 - 165 ppm)

O-alkyl C

(45 - 110 ppm)

humin*

9.9

19.5

20.7

HA

5.2 ± 1.0

52.2 ± 2.0

20.7 ± 1.4

7.4 ± 3.0

3.1 ± 1.0

70.0 ± 4.9

FA1

FA2

10.1 ± 1.3

4.2 ± 1.4

56.3 ± 2.1

FA3*

11.8

14.0

32.0

FAIHSS

10.2 ± 3.7

20.0 ± 3.3

25.4 ± 2.0

: aromatic C/ (aromatic C+ O-alkyl C+ alkyl C).

: The data was from one sub-horizon sample occurred between 162 and 167 cm depth.

Alkyl C

(0 - 45 ppm)

41.5

21.0 ± 1.4

18.2 ± 1.9

27.2 ± 0.8

41.6

44.0 ± 5.7

0.24

0.56 ± 0.03

0.04 ± 0.01

0.05 ± 0.02

0.16

0.23 ± 0.04

Table 5. The rate of vertical translocation of humin, humic acid (HA), hydrophilic fulvic acid (FA1 and

FA2), and hydrophobic fulvic acid (FA3 and FAIHSS) fractions prepared from eight sub-horizon samples

from a buried humic horizon occurred between 147 and 187 cm depth of an Andosol near Towada

volcano.

Sampling

depth

(cm)

147-152

152-157

157-162

162-167

167-172

172-177

177-182

182-187

average

humin

0.0

0.0

1.4

0.2

0.4

0.0

0.6

1.7

0.5

Rate of vertical translocation (mm/century)a

HA

FA1

FA2

FA3

0.0

0.0

0.0

0.0

0.0

0.2

0.1

0.5

0.1

**

**

**

0.0

**

**

**

2.4

2.7

4.0

4.0

3.6

3.3

**

2.7

1.5

2.7

2.5

4.4

2.3

**

4.5

3.9

3.6

3.8

FAIHSS

0.0

**

1.5

0.2

1.9

-*

2.5

1.6

1.3

The minimum rate of vertical translocation was assumed to be zero.

: (current depth of SOC fraction – depth of original deposition)/14C age of SOC fraction.

*: The rates of vertical translocation of FA2 (152 - 157 cm and 162 - 167 cm depths) and FAIHSS (172 177 cm depth) were not calculated due to low yield.

**: SOC fraction younger than the overlaid Towada-Chuseri pumice (5.39 ± 0.14 kyr BP) was not

considered in the calculation.

...