Overview

Basic OxidationReduction Chemistry

Mike Vepraskas
NC State University

1. Discuss basic oxidation

principles
2. Review principle types of
features formed by the reactions
3. Review how the reactions
change soil colors

Chemistry of Saturated
Soils
We will focus on OxidationReduction (Redox) reactions

What process formed this pattern?

These reactions are the most

important reactions in
saturated soils

Redox Reactions
influence::
Soil Colors
Organic matter
decomposition rates
Amounts of O2, NO-3, and
SO=4 in soil water

Redox Reactions transfer electrons

and protons among atoms

Proton
in nucleus

Atom

Oxidation Reduction Basics

Electrons are taken out of
one substance and given to
another
Most electrons (e-) come from
organic matter as it rots or
decomposes

electrons

Remember!
If organic matter is not present,
then:
1. The special redox reactions that
make soils anaerobic wont occur,
and
2. Saturated soils wont turn gray in
color

Oxidation-produces e- when
two things are present:

e- produced when organic

matter is eaten

e
+
H
Organic Matter

Organic Matter
Bacterium

Bacterium

Reduction-reactions with
e- and H+

O2 +
air

4e-

4H+

Oxidation and Reduction

occur together

2H2O

water

O2

air

H+
H2O
Oxidation

Reduction

When air is present in

soil, then

O2 penetrates
to here
Air cant
enter
saturated
soil

All e- produced by organic

matter decomposition are
grabbed by O2 to make
water

What happens in
waterlogged soils?
In waterlogged soils,
O2 (air) does not enter soil
because soil pores are filled
with water

But
Organic matter continues to
decompose in waterlogged
soils, but e- produced are
grabbed by:

NO3-, MnO2, Fe2O3, SO4=,

and CO2
These are used instead of O2

Remember

Reduction in waterlogged
soils

The electron acceptors

are reduced in a specific order:

1. O2
2. NO33. MnO2

4. Fe2O3
5. SO4=
6. CO2

NO3-

H+

N2
Oxidation

Denitrification
2NO3- + 10e- + 12H+
Nitrate

N2 + 6H2O
gas

Reduction

Iron Reduction
Fe2O3 + 4e- + 6H+
Iron oxide
(Red solid)

2Fe2+ + 3H2O
Reduced iron
(Colorless in solution)

Sulfate Reduction
SO42- + 8e- + 10H+
(in solution)

H2S + 4H2O
(smelly gas)

H2S smells like eggs

Reduction and
Swamp Gas

(carbon
dioxide gas)

CH4 + 2H2O

(methane gasburns)

O2

O2
ot
Ro
ad
De

CO2 + 8e- + 8H+

Air - Filled Pore

O2
H20

O2 only Electron Acceptor

Water - Filled Pore

What does Reduced

mean?

=
SO
H2S
4

ot
Ro
ad
De

Reduced forms of:

NO
N23

Fe(OH)3

HO22O

Oxygen (H20), Manganese(Mn2+)

2+
Nitrogen (N2) Iron (Fe ), or
Fe2+

Ususally focus on Fe2+

If Fe2+ is present in solution, then:
Oxygen has been reduced to
water: soil is anaerobic,
Nitrate denitrified,
Manganese reduced, but
Sulfate and CO2 may be oxidized

Sulfur (H2S)

are in the soil solution.

Assessing Soil Reduction

1. Analyze soil solution
chemistry
2. Use dyes (detect Fe2+)
3. Measure redox potential
4. Oxygen probe (detect O2)

Dyes detect Fe2+

, -dipyridyl (red color)
K3Fe(CN)6 (green color)

Good for routine use in FIELD

Apply dye to wet samples

in field

Redox Potential
Voltage measured between a:
Pt (platinum) wire, and
Reference electrode
Red color shows
Fe2+ present and soil
was anaerobic

which are both in contact with

the soil.

Volt meter

Redox Potentials

456

Redox Potential (mv)

Pt wire

Redox Potential (mv)

Reference
electrode

800
600

Oxidized soil
(Fe3+)

400
200

Reduced soil
(Fe2+)

0
4

pH

Voltage measured must be

adjusted with a correction
factor.
Voltage that identifies
reduced soil conditions
varies with pH.

800

Reduced Soil
Eh of 200 mv
pH of 5

600
400
200

0
4

pH

Uses of Redox Potential

Redox potential can tell
whether any soil is reduced
or oxidized at any time of
year.

Redox Potential (mv)

Saturation
O2
H 2O

500

170

Fe3+
Fe2+

1. Organic matter must be

present (source of e-)
2. Air must not enter soil
(soil must be saturated)

Gray
colors
form

0
-150

SO42H 2S
October

Conditions needed to
Reduce Iron Oxides

Organic C
increases

January

Sulfate
March
reduction
begins

Conditions needed to Reduce

Iron Oxides contd.
3. Bacteria must decompose organic
matter (Temps.> 42o F)
4. Dissolved O2 in water must be
removed (soil is anaerobic).
5. Nitrate and Mn oxides cant be
present either.

10

Good Kinds of Organic

Matter for Reduction
1. Dead roots (still squishy)

Reduction occurs where

bacteria eat organic matter
This can be in spots
(microsites) or around roots

2. Plant debris (leaves)

3. Dissolved organic matter

Fe reduction and anaerobic

soil were occurred here

Entire horizons will not be

reduced at one timeunless
saturated for long periods

Fe reduction and anaerobic

soil occurred around roots

11

Is this water
Fe-reduced
or anaerobic?

Is this water Fe-reduced or anaerobic?

Reduction occurs where

water moves through soil
slowly
Reduction is slowed
when water is flowing
Reduction occurs
quickest in stagnant
water

Soil horizon saturated

with moving water
water

O2

O2

O2
O2

O2
Reduced microsite
(anaerobic soil)

12

Jurisdictional Wetlands
must meet 3 Parameters:
Wetland Hydrology
Hydrophytic Plants
Hydric Soils
Lets turn to wetlands

Hydric Soil Definition

Soils that formed under
conditions of saturation
flooding, or ponding that
lasted long enough during the
growing season to develop
anaerobic conditions in the
upper part.

Hydric Soils are identified in

the field by:
Signs or field indicators that
form only in anaerobic or
reduced soils
Indicators usually have unique
colors formed in anaerobic
soils.

13

Overview

Soil Colors are changed by

two major processes:

1. Discuss basic oxidation

principles
2. Review how the reactions
change soil colors
3. Review principle types of
features formed by the reactions

Iron Reduction Effects on

Color
Iron oxides (Fe3+) are like
rust: theyre solids that create
red, yellow, and brown colors
Reduced iron (Fe2+) is
colorless and dissolves in
water

Organic matter
accumulation (makes soils
blacker)
2. Iron reduction (makes gray
and red mottles)
1.

Remember
The reduction of iron
oxides dissolves reddish
colors and turns the soil
gray.

14

Red Soil

Gray Soil

sand

Remove
Where
does the
reddish color
come
from?

Fe coats
Gray sand
covered
by red
Fe3+ coating

Sand
without
Fe coatings

Gray Soil Colors

Gray color comes from stripped

quartz grains

Gray colors have chromas

of 2 or less, and values of
4 or more.
Gray colors form when
iron oxides stripped off
particles

15

Gley Soil Colors

Gley colors are not gray colors.
gley

Gley colors

Gley Soil Colors

Gley colors are formed by
minerals that contain reduced Fe
(Fe2+)
They are rare, and may be found
only in reduced soils.
May need carbonates (shells),
sulfates, or phosphates to form.

gray

Gley colors are found on the

Gley pages of Munsell Color
Charts.

Gley vs Gray
Gray colors are permanent
throughout the year.
Gley colors may only be
present when soil is
saturated and reduced.

16

water

How do
Gley colors
form?

Topsoil

Subsoil

Gley colors come from

Reduced minerals, not stripped quartz

water

water

Topsoil

Topsoil

Fe reduced
in microsite
of A horizon
in marsh

Soil contains
carbonates
Subsoil

Fe2+

Subsoil

Fe2+

Root
channel
Carbonates
and shells

Reduced Fe moves
down root channel
into subsoil

17

Channel

Fe2+
Fe2+

Gley-colored
minerals in
horizon
that contains
carbonates

Gley color along

channel produced by
FeCO3 minerals.

Soils that have been

saturated and reduced:
Usually have a mixture of gray
and red colors in them.

Gray colors show where Fe

was reduced and removed.
Reddish colors (yellow and
brown too) show where it was
oxidized and accumulated.

18

Do gray colors always mean a

soil has been reduced?
Mixture of
gray and
reddish
colors shows
soil was
saturated
and reduced.

Remember!

NO!
Some parent materials never
had iron oxides in them, and
have always been gray in
subsoil.

Importance of a Colors

Chroma
Soils that were saturated
and reduced:
Usually have a mixture of gray
and red colors in them.

When chroma is < 2 :

Soil particles have no Fe
oxides on their surfaces
Soil may be reduced for
significant periods

19

Importance of a Colors

Chroma
When chroma is > 2 :
Soil particles have some Fe
oxides on their surfaces
Soil may be reduced for
short periods, but
May be saturated for significant
periods

Summary of Major Points contd.

3. The percentage of gray color is

related to how long a soil is
reduced, not how long its
saturated.
4. To find out how long a soil is
saturated you must measure water
table levels with a well.

Summary of Major Points

1. Oxidation-reduction reactions
cause gray colors to form in soils
that are saturated and reduced.
2. Redox reactions need organic
matter, bacteria, and no air (O2) to
create gray colors.

Overview
1. Discuss basic oxidation

principles
2.Review how the reactions
change soil colors
3. Review principle types of
features formed by the reactions

20

Indicators of Reduction
What signs
are here that
show the soil
was saturated
and reduced?

Element

O2
Fe3+
S

Hydric Soil Field Indicators

1. Are the indicators of
Reduction
2. Are formed by the:
--accumulation of C,
--reduction of Fe and Mn,
--reduction of SO4

When reduced we get:

Carbon (muck)
accumulation
Redoximorphic
Features
Rotten egg odor

Carbon-Based Indicators
Organic matter builds up when
soils are saturated and
reduced because:
Decomposition is slower than
production

21

C-Based Indicator Types

Layers of Organic Material

20 cm muck

Organic soil
layer
(C-indicator)

C-Based Indicators in Mineral

Soils
Dark Surface: color value <3,
chroma <1
Black coatings on sand grains
Mucky mineral layers (e.g. mucky
sandy loam)

Layer Thickness
>16 in.

Indicator Name
Histosol or organic soil

8- 16 in.

Histic epipedon

<8 in.

Layer of peat or muck

Comments on C-Indicators
Indicators are permanent
Carbon occurs in most soils and
indicators are common
These indicators are essential
where soils have little Fe.

22

Iron-Based Indicators:
Redoximorphic Features
Features that are formed by the:
Reduction,
Movement, and
Oxidation
of Fe and Mn oxides

23

Comments about

Redoximorphic Features
Features are widespread and are
found in most soils
Most are permanent
(last 1 year or more)

Sulfur-Based Indicators:
Formation
H2S

SO42Odorless,
In solution

Rotten-egg odor

All need Fe or Mn to form

Comments on

S-Based Indicators
Only detected when soil is
reduced and saturated
Rarely used in field compared to
others
Difficult to identify exactly

Summary
1. Oxidation-reduction reactions
cause soil colors to change when
soils are saturated.
2. These reactions require:
bacteria,
organic matter,
saturated soil, and
stagnant water.

24

Summary contd.
3. Indicators that show these reaction
occurred are composed of Fe, Mn,
C, and S.
4. Reduction processes form
indicators, saturation by itself does
not create indicators of reduction.

The End

25