Soil Chemistry

Transfer vs transformation in Env

2

—  Transfer involves a change in location

¡  E.g water falling as rain, running off the land into a river then
to the sea

—  Transformation involves a change in state

¡  E.g evaporation of water from the lake into the atmosphere
 Transfer vs transformation in soil
3

—  Transfer involves a change in location

¡  Change in concentration of pollutant due to transport process
(diffusion, advection, volatility)
¡  Can be single process or simultaneously

—  Transformation involves a change in state

¡  Change of pollutants : concentration, physic and chemical
properties
¡  Locations: interface between particles and pollutant or in soil
solution
¡  Weathering (pelapukan) and plant- uptake
Possible reaction in soil
4
5
 Availability of ions (nutrients) in soil
6

Decrease Increase
—  uptake by plants —  addition of fertilizer
—  leaching —  decomposition of plants
—  conversion into insoluble —  manure
forms —  dissolving of rock
 Example
7

—  Bila dalam 2 L larutan mengandung 2 g NaOH,

tentukan molaritas larutan.
(reporting of 2 g NaOH in 2 L solution, determine the
molarity)
 8

—  Concentration in solution

mg/L, µg/L
millimole (mM), µmole (µM)
part per million (ppm), part per billion (ppb)
Molarity (M) = mole contaminant/L solution

Soil Analysis Ch5

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ppm and mg/l

ppm = mg contaminant/kg medium
ppm = mass of contaminant/(mass of medium x 106)
ppm=mg/L akan benar kalau temperatur 4C dimana
densitas water 1000g/L, pada temp 25 C 0.997 kg/L

Bila ada larutan dengan konsentrasi 1000 mg/L pada temp

4C, maka konsentrasi 1000 ppm, tetapi pada 25C konsentrasi
menjadi:
1000 mg/L x L/0.997 = 1003 mg/kg = 1003 ppm

Soil Analysis Ch5

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—  Concentration in sludge (soil)

mass of contaminant/mass of soil = mg/kg, µg/kg

•  Concentration in air
mass of contaminant/vol of mass air = µg/m3
ppm = vol of contaminant/ 106 vol of air
•  Radioactive
milli Curie (mCi), µCi

Soil Analysis Ch5

 Unit concentration in soil
11

Soil Analysis Ch5

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 Soil pH
13

—  one of its most important properties

—  it affects so many other soil properties, (eg ion exchange
and nutrient availability)
—  soil pH comes about from a balance between acidic and
alkaline species
—  reflects mainly the levels of dissolved H+ and OH-, but
also the adsorbed H+ on cation exchange sites
—  normally ranges from 4-9.
di Ind 4-7, untuk gambut (peat) <4.
pH tanah kapur > tanah vulkanis (di lembang 4-5)
Nilai pH tanah lebih tepat nilai pH dari larutan tanah
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Soil Analysis Ch5

16
17
 Sources of soil acidity
18

—  rain - polluted or fresh will be slightly acidic due to

dissolved gases

—  microbial and root respiration – this produces CO2,

which is slightly acidic in solution

—  oxidation of organic matter – this produces organic

acids known as humic acids, together with nitric and
sulfuric acids
 Sources of soil alkalinity
19

—  carbonate minerals – calcium and magnesium carbonate

are common materials in minerals
—  they are slightly soluble in water, and produce OH- as
they dissolve
—  these cations and Na & K are known as bases because of
their association with alkaline soils

—  mineral weathering- – many primary minerals as they

weather release hydroxide salts of the basic cations
 Trends in soil pH
20

—  as soils age by weathering and leaching, they tend to

become more acidic
—  primary minerals that release alkaline materials are
replaced by neutral or slightly acidic secondary
minerals
—  leaching removes the carbonate minerals
—  weathering occurs from the surface downwards so
that the A and B horizons will tend to be more acidic
than the C horizon
 Significance of soil pH
21

—  nutrient availability – the ability of plants to take

up nutrients is very much dependent on the soil pH

Soil Analysis Ch5

 Significance of soil pH
22

—  effect on soil organisms – soil organisms prefer

different pH levels
—  acid-sulfate soils - soils that are rich in inorganic
sulfide minerals, such as pyrites,
¡  can lead to the formation of excessive levels of sulfuric acid
through oxidation
¡  soil pH dives to very low levels
¡  causes solubilisation of toxic levels of aluminium, manganese
and iron from soil minerals
—  plant preferences – most alkaline soils; a few which
need acidic soils
 Soil pH importance
—  Determines solubility of
nutrients
¡  Before plants can get
nutrients, they must be
dissolved in soil solution

—  Microbial activity also

depends on pH
 General soil pH conditions:

“Slightly acid” “Slightly basic”

6.0 – 6.6 7.4 – 8.0

“Moderately acid” “Moderately basic”

5.0 – 6.0 8.0 – 9.0

“Strongly acid” “Strongly basic”

< 5.0 > 9.0
 How we measure soil pH
25
—  Mix the soil with solution (H2O, 0.01 M CaCl2 or 1 M
KCl)
—  Ratio soil:water = 1:1, 1:2, 1:5, 1:10
—  Measure pH of solution
—  Base on ISO 10930, soil quality-determination of pH
using glass electrode in a 1:5 (volume fraction)
suspension of soil in water (pH in H2O), in 1 mol/L
pottasium chloride (pH in KCl) or in 0.01 mol/L calcium
chloride solution (pH in CaCl2)
 Causes of soil basicity

1.  Hydrolysis of basic cations

2.  Hydrolysis of carbonates
 1. Hydrolysis of basic cations:
(especially Ca+2, Mg+2, K+, NH4+, Na+)

(also called exchangeable bases)

Extent to which exchangeable bases will hydrolyze

depends on ability to compete with H+ ions for
exchange sites.

Na Na Na Na
H 2O + + OH-
H Na
Na +
Na Na Na Na
 Clay Minerals
28

—  naturally occurring inorganic compounds

—  form initially in the crystallisation of molten rock
material
—  known as primary minerals
¡  eg olivine, quartz, feldspar and hornblende
¡  not stable when exposed to water, wind and extremes of
temperature
—  break down physically and chemically
—  reform and crystallise in a different structure
 Clay minerals
29

—  called secondary minerals

¡  eg vermiculite, montmorillonite and kaolinite

—  tend to be much smaller in particle size than primary

minerals
—  most commonly found in the clay fraction of soils
—  only the youngest and unweathered of soils will not
contain mainly secondary minerals
 The Earth’s
30
crust

Ca
Al Fe

Si K
Mg
Na

Others

O
Soil Analysis Ch5
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—  oxygen is negatively charged

—  the other major elements are positively charged
—  oxygen bonds with one or more of the cations,
producing a chemistry of oxides
¡  silicon oxides (silicates)
¡  aluminium oxides (aluminates)

—  generally in combination as aluminosilicates

—  these dominate the minerals
—  low levels of other elements account for the
differences in minerals
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—  Si binds to four oxygens in a tetrahedron

—  Al has six oxygens (often as OH) in an octahedron
—  not a matter of individual SiO4 or Al(OH)6 units
—  some Os are shared between the silicate or aluminate
units
—  most common structure in clay minerals is the formation
of sheets
—  “flat” layers of silicate tetrahedra or aluminate octahedra
—  these sheets stack on top of each other
—  held together by hydrogen bonding or electrostatic
attraction
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—  real clay crystals are not pure silicates or aluminates

—  some Si or Al atoms are substituted during the
crystallisation process
—  creates spare charges which give the overall crystal a
charge
—  balanced by loose cations or anions
O has only 1 bond,
O O so has -ve charge;
Si replaced requires balancing
O Si O O Al O- positive charge from
by Al in crystal free cation
O O X+
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—  these cations generally are held on the surface of the clay
—  are not strongly held
—  can be exchanged for other cations in an equilibrium process
—  measured as the cation exchange capacity (CEC)
—  soil pH has no effect on the exchange capacity from the clay minerals
 35

—  as minerals weather (pelapukan), they lose silica

—  this leads to increasing proportions of aluminate in
weathered clays
—  Al-OH species are amphiprotic
—  soils dominated by oxides of aluminium (and other
metals) can have positive sites in acidic soils
—  this allows anion exchange

Al-OH + H+ <=> Al-OH2+ + X-

 Ion exchange in soils
36

—  when the loosely held cations or anions on the

mineral surfaces are replaced by ions of the same
charge (sign and magnitude) in solution
—  cation exchange is by far the most common
necessary for soil fertility
—  as soils weather, they lose cation exchange capacity
and lose fertility
 Cation Exchange
37

—  clay minerals have negative charge due to substitution of aluminium or

silicon in the crystal lattice
—  humus also contributes negative charge, due to the presence of
dissociated organic acids
¡  humus-COOH ↔ humus-COO- + H+

Exercise 5.2
—  What effect would soil pH have on the amount of
cation sites from humus?

—  low pH, less dissociated acid, less sites

 38

—  a cation in solution replaces an adsorbed cation on the

soil particle
—  eg soil-Na + K+ (aq) ↔ soil-K + Na+ (aq)

—  charges that are balanced, not number of charged

species.

Class Exercise 5.3

—  Write an equation for the exchange of adsorbed sodium
with solution calcium.

—  soil-Na + soil-Na + Ca2+ (aq) ↔ soil=Ca + 2Na+ (aq)

 39

—  exchange is equilibrium

—  reversible and dependent on the levels of each of the
species, particularly the solution species
¡  eg if a soil solution becomes depleted in calcium, then some
calcium will desorb from an exchange site into solution
—  known as buffering
—  in all but the most leached and infertile of soils, there
will be a balance between adsorbed and dissolved
ions
 Exercise 5.4
40

—  What do you think would happen to a soil which is

treated with lime (calcium hydroxide), in addition
to a pH change?

—  high concentration of Ca in solution

—  this would be partly reduced by exchange with the
soil cations
 Cation exchange capacity (CEC)
41

—  the moles of exchangeable positive charge per unit

mass 100 g of dry soil

—  usually mmole/100g or cmole/kg (the same value)

—  Ca & Mg contribute twice as much to the CEC as an

equivalent number of sodium and potassium ions
because of their 2+ charges

Soil Analysis Ch5

Soil CEC Class Exercise 5.5
—  Comment on the trend in CEC
Sand 2-4 in Table 5.1.

—  CEC increases with higher clay

Sandy loam 2-12
levels

Loam 7-16

Silt loam 9-26

Clay, clay loam 4-60

Soil Analysis Ch5

42
 Significance of CEC
43

—  uptake of nutrient ions from plant roots occurs from

solution only
—  as cations are absorbed into the roots, they are replaced
in the soil solution by H+ ions
—  when the exchange equilibrium is disturbed, some of that
ion will desorb from the soil particles
—  replaced by another ion
—  if the nutrient is a weakly adsorbed one, such as K, there
may not be enough adsorbed to replenish the soil,
presenting a fertility problem
—  K is the most likely cation to be in short supply

Soil Analysis Ch5

 Anion exchange
44

—  the important soil anions, nitrate and phosphate,

behave very different at exchange sites
—  nitrate and chloride are only weakly held at positive
sites
—  more likely to be found in soil solution
—  phosphate and sulfate are very strongly bound to the
exchange sites
—  phosphate can become covalently and irreversibly
bound

Soil Analysis Ch5

 Exercise 5.9
45

—  What factors will affect the amount of liming

required?

—  buffering capacity

—  pH
 Redox potential (Eh)
46

—  a measure of its ability to produce oxidation or

reduction of chemical species in it
—  the most important soil property indicated by the
soil Eh is whether it is aerobic or anaerobic
—  aerobic soils give a positive value
—  the lower the value the more anaerobic the
conditions
—  a value that is affected by soil pH
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Soil Analysis Ch5