Chapter 4B: Chemistry of the

solid earth
 Outline
• Chemical reaction in soil
• Soil processes
• Soil pollution
 Chemical reaction in soil
• 2 important chemical functions of a soil are:
– To supply nutrients to plants
– To act as a filter or sink for pollutants

• Process occurs at the interface between soil solution

and the solid phase
• Various mechanisms control the equilibrium between
chemical species in the 2 phases, with movement
between them being controlled by changes in solution
concentration
 1. Ion exchange (physisorption)
• The process where ions held at a charged
surface by coulombic bonding are
exchangeable with other ions of the same
charge in solution in contact with the surface
• Example:
– Cation exchange: Cations held at negatively
charged surfaces
– Anion exchange can occur, but is of minor
importance
 Cation-Exchange Capacity
• CEC of soil is a
measure of its
ability to hold
cations at
negative sites
by coulombic
bonds
• Unit: cmolc kg-1
or meq 100 g-1
 2. Ligand exchange (Chemisorption)
• The process by which ions are held at a solid phase
surface by covalent bonding
• Example: certain anions especially phosphate &
some trace metals (Fe & Al oxides)
• Often described by use of the Langmuir equation
 3. Complexation / chelation
• Inorganic / organic ligands are ubiquitous in
soils
• Large fraction of soluble metals may be
complexed
• Step wise stability constants
– M + L ⇌ ML K1=[ML]/[M][L]
– ML + L ⇌ ML2 K2 = [ML2]/[ML][L]
– MLn-1 + L ⇌ MLn Kn=[MLn]/[MLn-1][L]
 4. Precipitation / dissolution
• Solids can either be formed (precipitation) or
destroyed (dissolution) depending upon the
conditions of the solution.
• Factors affecting dissolution/precipitation in
soils are: ionic composition and concentration,
pH, and temperature.
• In addition, solution species that form strong
complexes with the constituents of a solid may
enhance the dissolution of such solids.
 Soil Pollution
• Major soil pollutants
– Heavy metals
– Pesticides
– Fertilizers (N, P)
• Major sources
– Pesticides & fertilizers
– Solid waste & sludge disposal
– Wastewater irrigation
• Accidental application includes:
– From atmosphere
• Acid rain
• Radioactive fallout
• VOCs
• Particulate deposition (PAHs, volatile metals)
– From below (buried sources, groundwater)
• Migration of landfill leachates
• Migration of spilled chemicals or leaking stored
chemicals
• Sewage spills or pipe leaks
Important Soil Environmental Processes

• Redox
• Hydrolysis
• Acid-Base reaction
• Heavy metals • Complexation/chelation
• Precipitation
• Sorption
• Pesticides • Biological degradation
• Physical process
(volatilization)
• Photochemical processes
Factors affecting fate of pollutant in soil
Pollutant

Physical process Chemical process Biological process

Bioavailability
Solubility, Bioaccumulation,
Oxidation,
volatilization… bioconcentration,
reduction,
Affect the adsorption, degradation
distribution complexation,
hydrolysis… Transformation process: increase
of chemical
chemical mobility
in soil 
affect
mobility Adsorption capacity:
Leaching potential to groundwater surface area, CEC, pH,
system temperature, chemical
properties
 Case study: HMs in soil around Bukit
Chuping, Kangar, Perlis
• Sahibin A.R. & Mohamad M.T. (2001)
Soil parameter analysis
HMs & major minerals
 Case study 2: Chlorpyrifos & malathion
residue in soils of a Terengganu golf course
 Hot topic: Carbon storage in soils
• The terrestrial biosphere is believed to be storing up to
50% of the CO2 released to the atmosphere from fossil
fuel burning
• Most of this C cycles through soils in organic and inorganic
forms
• Quantifying the net change in terrestrial biomass
(photosynthesis minus respiration) is essential for
understanding soil C flux changes
• There is much active research into the complex interplay
of nutrient supply / recycling and its effect on CO2 storage
 Global Carbon Cycle: Units
• Units:
1 ton = 1 x 103 Kg = 1 x 106 g

• 1 gigaton (Gt) = 1 billion tons = 1 x 109 tons

1 Gt = 1 x 109 tons
1 ton = 1 x 106 g
1 Gt = 1 x 1015 g = 1Pg (petagrams)
The Global Carbon Cycle
 Global Carbon Cycle: Pools
• Atmosphere: 750 Pg
• Vegetation: 610 Pg
• Soil: 1,580 Pg
• Fossil Fuels: 5,000 Pg
• Oceans (organic) 1,020 Pg
• Oceans (inorganic) 38,100 Pg
• Carbonate Rocks 1 x 106 Pg
Global Carbon Cycle: Fluxes (Pg/yr)
• Atmosphere to vegetation -61.4
• Vegetation to atmosphere +60
• Deforestation (loss) +1.6
• Change in land use -0.5
• Fossil Fuel combustion +5.5
In atmosphere: +5.2
 Atmospheric CO2 concentration trend
at Mauna Loa Station, Hawaii, U.S. (1958-
1996)
 Summary
• Chemical reaction in soil
• Soil pollution