Soil Organic Matter Its Characteristics and Roles in...

Soil Organic Matter Its Characteristics and Roles in

Agricultural Environments Part 4

Kiyoshi Tsutsuki

Obihiro University of Agriculture and Veterinary Medicine

Characterization of soil organic matter

Division of soil organic matter（Takai, 1977）

Soil Organic Matter

Biota Non-biota

Dead body of biota Dark amorphous high polymer

Animal and microbial residue Plant residue

Non-humic substances Humic substances

Humus

Soil

Extracted solution Residue

Acid

Supernatant Precipitate

Humin Humic acid Fulvic acid

Alkaline extractant

HFdecompo

sition

Chelating

agent

Fractionation of humic substances

Proposed molecular structure of humic acid

Chemical composition of soil organic matter

Molecular weight

Complexity Dark color

Organo-mineral complex Coarse OM

Water soluble OM

Humic

Humin Humic acid Fulvic acid

Soil organic matter

Heterocyclic N, Nucleophilic N Protein, peptide Nucleic acid Amino acid

Cellulose Hemicellulose Monosaccharides

Resin Suberin, cutin Triglyceride Higher fatty acid

Sterol Lower fatty acid

adsorbed

Non-adorbed

Peptideglycan

Phospholipid

Non-humic

Interaction with inorganic components

Humic and non-humic concept

According to solubility

Co-existing non-humic substances

Lignin

Phytic acid

Non-humic

Large small

Plant constituents Low molecular weight Humic substancesdegradation products

Lignin Polyphenols Brown polymerTannin QuinonesCellulose Monosaccharides MelanoidineHemi-cellulose Aminoacids, Amino sugars CalamelProtein Fatty acidsFat, Resin Fulvic acidSterols Degrading High-polymerFlavonoidsFree phenols Lignin

Protein Humic acidMicrobial constituents Polysaccharides

Resins Rp type

Peptide-glycane B type, P0 Type

Teicoic acid Atype, P+ Type

Muco-polysaccharidesLipo-protein Dark-colored high-polymer HuminPhospho-lipids

Igintion residue of plants

Non-biotic oxidation and polymerizationby catalytic action of volcanic ashes,clay minerals, and metal oxides

Figure 1. Synthetic pathways of humic substances

Min

eral

s

Synthesis and degradation by microbes

Mic

robe

s

Humic acid

Humin

Fulvic acid

Water soluble OM Free form OM

Humic substance Non-humic

Concept on soil organic matter

Soluble in acid and

alkaline

Not soluble in alkali

or acid

Precipitate with acid

Bound with minerals

Dark colored, amorphous high polymer OM with known structure

Not bound with

minerals

Soluble in water

COO-

COO-

COO-

COO- COO-

COO-

COO-

COO-

OH

OH

OH OH OH

OH

OH

OH

COO-

COO-

COO-

COO-

-OOC O O

O

O O

O O

O

O O

Hydrophilic part

Hydrophobic part

Carbohydrate

chain

Condensed

ring

Turbostratic

structure

Structural concept of humic substances

NH3+

Protein

CO

CO

CO

CO

CO

CO

CO

OC OC

Synthetic expression of elementary composition of humic substances

• As indices for expressing elementary composition synthetically, following ratios are calculated. Elementary number is used in the calculation.

Combustion Quotient

• Combustion quotient (CQ) is a theoretical value for respiration quotient as proposed by Tamiya 5)

• CQ= 4C / (4C + H－3N－2O) ------ (1)

Degree of Unsaturation

• Degree of unsaturation ( DU) shows the number of unsaturated bonds and ring bonds per 100 carbon atoms.

• DUH = (2C + N－H) / 2C ×100 ------ (2)

Degree of Oxidation (ω)

ω＝（2O－H）/ C ------ (3)

shows the excess or deficit of oxygen and hydrogen in comparison with Cn(H2O)n

• This value is distributed between －0.8 and +0.9 for humic substances.

Elementary composition of humic substances H/C and O/C

0.00

0.20

0.40

0.60

0.80

1.00

1.20

1.40

1.60

1.80

0.00 0.20 0.40 0.60 0.80 1.00 1.20

H/C

O/C

Soil

Buried soil

Environmental

Sedient

Sed-Humin

Coal

Orl-HA

Orl-FA

0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

1.8

-1.0 -0.5 0.0 0.5 1.0

H/C

Degree of oxidation ω

Degree of oxidation(ω) and H/C ● soil humic acids from literature 3 ■ humic acids from buried volcanic ash sois、○ humic asids from literature 7, △ humic acids from sea and lake sediments, ▲ humin from sediments, □ coal, ◆ humic acids from Russian soils in literature 6 ◇fulvic acids from Russian soils.

0

40

80

120

160

0.30.50.70.91.1

RF

Δ logK

A型

B型

Rp型

P型

0

40

80

120

160

0.30.50.70.91.1

RF

Δ logK

Classification of humic substances by RF and ΔlogK ● Type A, ○ Type B, ■ Type P with obvious Pg absorption, □ Type P without Pg absorption ▲ Type Rp from mineral soil, △ Type Rp from O layer

Type A

Type B

Type

Rp Type P

UV-vis. Absorption spectra of humic acis in different types Type A Inogashira (volcanic ash soil), Type B Higashiyama (brown forest soil), Type P Tsubame (Pg of buried soil), Type Rp Anjo (paddy soil) Concentrations are adjusted to 1mgC mL-1

0.1

1

10

100

200 250 300 350 400 450 500 550 600 650 700

ab

sorb

an

ce

nm

A型

B型

P型

Rp型

pH12-pH7 difference absorption spectra of different types of humic acids. （Same humic acids as in the previous figure）

-2

-1

0

1

2

3

4

5

200 300 400 500 600 700

pH

12-pH

7 d

iffe

rence a

bso

rption

nm

A型

B型

P型

Rp型