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responsible for the high reactivity of colloidal particles comparing with other soil particles. High reactivity of colloids mean: 1- High Adsorption Capacity Adsorption of H2O, cations, anions & soluble molecules due to high surface area 2- High Cation Exchange Capacity (CEC). Due to negative electric charge exists on the surface of colloidal particles. Colloidal particles play an important role in: 1 - Physical and chemical characteristics of soil. 2 - Plant nutrition, and
- According to their origin, soil colloids could be divided into two types: * Inorganic or Mineral Colloids: Originated from the decomposition of rocks and mineral of the parent material. Inorganic colloids include; - Secondary clay minerals, aluminusilicates, phyllosilicates, layer silicates (all are synonymous to the same object) - Hydrous oxides (oxides, hydroxides and oxy-hydroxides) of Fe, Al and Mn (Sesquioxide) - Amorphous or non-crystalline materials (Allophane, Imogolite) * Organic Colloids (Humus): Originated from the decomposition of debris and bodies of all living organisms after their death. Among all living organisms exist either on the surface or subsurface the soil, green plants are the most dominant component of soil organic colloid.
(SiO4)
-4
Tetrahedral units bounded together to form Tetrahedral Sheet (silica sheet) of formula )Si2O5)2-
-2
{Al(OH)6}
-3
{Al2(OH)6}
s s s
Tetrahedral sheet bounded to octahedral one in different ways to form one layer. Secondary clay minerals consist of high number of layers. Each layer contains certain number of sheets. According to the number of sheets exist in the layer, secondary clay minerals are typified to three groups:
Tetrahedral sheet
0.72 nm
Hydrogen bond exists between oxygen atoms of the upper layer and hydroxyl groups (OH) of the lower layer
Octahedral sheet
(OH)
Hydrogen bond exists between oxygen atoms of the upper layer and hydroxyl groups (OH) of the lower layer
O O
Characteristics of Montmorillonite mineral: 1- Expanded mineral due to weak bond (O-O) between layers. Explain Why? 2High CEC varied between 80-120 Cmol(+)/kg. Give reason. 3- High specific surface area (700 m2/g). Give reason.
Montmorillonite
Kaolinite
O O
O OH
Expanded Mineral
None-Expanded
1- Permanent Charge
Created from isomorphous substitution through: - Replacing of Si4+ in tetrahedral sheet by Al3+ - Replacing of Al3+ in octahedral sheet by Mg2+, These replacements lead to a creation of negative charge on the surface of clay mineral.
Isomorphous substitution
O O
Si
O
8
Variable charge Permanent charge (broken edges, (Isomorphous unsatisfied Valence) substitution) Low CEC ( 5 15 Cmol+/kg) Low SA (10-20 m2/gm) High CEC (80 120 Cmol+/kg) High SA (~ 700 m2/g)
Clay Minerals
Inorganic Soil Colloids also include; - Hydrous oxides (oxides, hydroxides and oxyhydroxides) of Fe, Al and Mn (Sesquioxide). Exist in highly weathered soil (tropical regions) - Amorphous or non-crystalline materials (Allophane, Imogolite)- Mainly exist in soil formed on volcanic rocks.
II - ORGANIC COLLOIDS
Soil Organic Matter
HUMUS
s s s s
Sources and chemical composition of organic matter Decomposition of OM Humus formation Chemical properties of humus: Effect of humus on soil fertility
6 - Enhances formation of stable soil aggregates and overall soil structure that affect air and water relationships. 7- Increase cation exchange capacity (CEC), and adsorption capacity of soil. 8 Plays an important role in decontamination of heavy metals and pesticides. 9 Increasing soil buffering capacity. 10- It protects the surface of soil from erosion.
- In mineral soils, the quantity of organic matter (OM) varied between 0.5 5%. - In alluvial soils of Egypt, OM content ranged from 1 3%, whereas, OM content in sandy soil is less than 0.5% - In organic soil, the quantity is usually higher than 18%. - Organic matter is determined in soil and calculated in form of organic carbon (OC). - A conversion between SOM and SOC could achieved using a factor represent the percent of C in OM ( average about 58%) - SOM = OC * 1.72 ( also this factor could used as 1.8 or 2 ) - The quantity of organic matter in soil decreased with depth ( Fig. ).
Chemical composition of fresh organic matter: Compounds released in soil by the death of plants and living organisms are;
1 Carbohydrates: (polysaccrides, starch, hemicelluloses and cellulose) 2 - Proteins 3 - Tannins 4 - Wax and fats 5 - Lignin.
Humus formation:
The modified lignin that resist microbial decomposition combined with microbial protein that formed inside microbial cells and released to the soil after the death of microbes, to form humus. It is just one assumption or a theory for formation of humus in soil. (There are many theories dealt with humus formation).
Two important processes take place during the decomposition of organic residues. These two processes are Mineralization and immobilization. They exist side by side, but the dominancy of one of them depends on chemical composition of organic residues, particularly the ratio between C and N in the residues (C:N ratio).
Mineralization process
- Mineralization means transformation of nutrients from organic form (unavailable to plant) to simple mineral form available to plant. - Nutrients are released in simple mineral form (e.g., NH4, NO3, K,..) available to plants when C:N ratio of the organic residues fall down to 20:1 or lower.
So, organic residues with C:N ratio higher than 33:1 should be decomposed in piles before addition to soil until C:N ratio dropped to be less than 33:1. Residues of C:N ratio of 20:1 or lower is most suitable for addition.
Chemical Composition of humus: Chemical composition of humus are not well known yet. Three components could be obtained from humus when submit to extraction using strong bases and acids: 1- Humin 2- Humic acid (HA) 3- Fulvic acid (FA)
Properties of Humus
These functional groups are responsible for high reactivity of humus comparing with other particles exist in soil. They are responsible for: 1- Electrical charge created on humus. 2- Exchange and adsorption reactions, and 3- Chelation and complex formation between humus and metal cations.
Humus contains also amine groups (R-NH2) This group is amphoteric. This group has the ability to gain a proton (H+ ion) and carries positive charge (+). R-NH2 + H+ R-NH3+ Also, this group can carry negative charge at higher pH values through ionization of H+ ion. R-NH2 + OH- R-NH+ H2O
Reactivity of colloids could be explained through the two important reactions (processes) take place on their surface; 1 Ion Exchange Reaction 2 Adsorption Reaction
The ions attracted to the colloidal surfaces by electrostatic attractions called Exchangeable Ions.
-
These ions can be replaced by others have similar charges through a replacement process called Ion Exchange Reaction.
-
The exchangeable cations in soils are usually bases like, Ca, Na, Mg and K. However, in acidic soils, Al3+ and H+ are exist as exchangeable cations besides bases ones. - When negatively charged ions attracted to sites have positive charge, the process called Anion Exchange, and ions called Exchangeable Anions. Anion exchange reaction is rare in soil, and may exist in acidic conditions rather than normal or slightly alkaline soil. - The sum of exchangeable cations satisfy the negative charge sites on the surface of colloidal particles called Cation Exchange Capacity, CEC Defintion: Cation exchange capacity is the sum of all exchangeable cations satisfy the negative charge of soil particles at pH 7.0, or any other given pH, and calculated in [Cmol(+)/kg]. (The old units was meq/100g).
Cation Exchange Capacity of soil increased as pH increased based on the fact that part of negative charge is variable, or, pH dependent charge which is dependent on pH.
Soil Characteristics Based on Ion Exchange Process & The Environmental Significance of the Process
pH = - [Log H+]
In generally pH scale ranged from ( 0 14)
-But, soil pH varies between 4 -10. * Soils around the world have different pH values and could be typified according to pH value to: I - Arid and semi-arid regions, like Egypt and all Arab countries, soil usually have pH higher than 7 and up to 8.5. These soils called alkaline or slightly alkaline soil. -(in some cases, pH gets higher than 8.5 and could reached 9 or 10. This soil called alkali soil or sodic soil. This soil cant be cultivated (unproductive soil), and needs reclamation.
Fuel and waste Burning: Variable gases are produced through burning of fuel and wastes. These gases cause air pollution, so, the air of industrial regions and crowded cities is loaded by abnormal concentrations of CO2 , NO2 and SO2 which dissolve in rain water to produce the phenomenon called "Acid Rain" according to the following equations. CO2 + H2O H2CO3 CO3 + + 2 NO2 + H2O HNO3 NO3- + H+ These gases are additional sources of H+ ion in soil system
s s
Inside each group previously mentioned, Soil pH varied as the following factors varied; 1- Soil organic matter: Soil pH decrease as OM% increased. 2 - CO2 concentration in soil air: Soil pH decreased as CO2 pressure in soil-air increased, particularly in calcareous soil. 3 - Suspension effect: As soil: solution ratio increased, soil pH increased. 4 - salt concentration: As salt content increased, soil pH desreased. 5 - Kind of exchangeable cations:
Practical Issue
Kind of Exchangeable Cations Base saturation percent (BS%) BS% = { [Na + K+ Ca + Mg]ex / CEC )} X 100 1 - If all exchangeable cations are bases (Na, K, Ca, Mg), soil pH is higher than 7. Under this situation, If exchangeable Ca is predominant (represent at least 80% of all exchangeable cations CEC), the pH usually lies between 7 8.5.
If exchangeable Na percent (ESP) increased to be 15% or more of CEC, the pH value will increase to be higher than 8.5, and the soil became alkali or sodic soil. (i.e., The magnitude of increases of pH depend on the type of bases. Strong bases (e.g., Na+) highly increase pH. Whereas, weak bases (e.g., Ca2+ & Mg2+) slightly increase the pH value. On the other hand, if BS% decreased to be less than 100%. Which means that acidic cations (H+ and Al3+) are exist as exchangeable, the soil pH decreases to be lower than 7. Then, the soil is acidic.
Na Ca
PH
BS% So, Ca2+ is preferred than Na+ to be exchanged in soil. Exchangeable sodium percent could be obtained as follows: ESP = { [Na+]/ CEC} 100 As ESP increased to be 15%, soil-pH will increases and exceeds 8.5. Then, the soil becomes sodic or alkali.
Problem on base saturation percent (BS%) A soil containing the following exchangeable cations (Cmole/kg) Ca = 8 , Mg = 3, Na = 8, k = 2 Calculate the following: 1- CEC 2 BS% 3 ESP 4 - How to modify its pH?
Definition: soil buffering action is the ability of soil to resist changes in pH due to the addition of acids or bases. Types & Mechanisms of soil buffering : 1- chemical buffering: due to the reaction of soil constituents with the added acids or bases. - An example, by the addition of acid to calcareous soil, the soil pH does not change due to the direct chemical reaction between the added acid and calcium carbonate as follows: CaCO3 + 2 HCl CaCl2 + H2O + CO2
So, calcareous soil has high buffering action for acids additives.
SBA
s
s
2- Compensation buffering:
this type of soil buffering is depending upon the presence of soil colloids (humus & clay minerals) and the equilibrium between active and exchangeable acidity (i.e., between H+ exist in solution and exchangeable H+ as follows:
+
Compensation
Base added
Reservation
+ Hac
active acidity 0.1%
OH+
H2O H
Acid added
According to the "Law of mass action" the increases of H+ concentration in solution as a result of addition of acid, will shift the direction of the reaction to left side. This means that the excess soluble H+ ions will be changed to exchangeable form (reservation reaction) and the pH remains almost constant. On the other hand, the decrease of active acidity by the addition of bases (OH), the reaction should be shifted to wright side by compensation process. This means that some exchangeable acidity will be released from DDL to the soluble form which keep the pH unchanged.
Definition: SBC is the amount of acid or base (mole or meq) required to change the pH of the mass unit of the soil by one unit. 1 - Soil texture: As clay percent increased, SBC increased. 2 - Organic matter content: The increase in OM content is accompanied by an increase in SBC. 3 - CEC: The higher the soil CEC , the higher the SBC. This could be attributed to the high reserve acidity which can compensate any shortage in soluble H+ . 4 - Calcium carbonate content: Presence of lime in the soil increases SBC especially against acidic additions.
-Acidic soils characterized by high percent of exchangeable H+ and Al3+ which lead to sharp decrease in pH value. The soil became unsuitable for plant growth. Acidic soils could be reclaimed by addition of lime as a source of Ca cation this process called liming - lime dissolves in the acidic condition and produce Ca2+ cations. The produced Ca2+ replaces H+ and Al3+ in surface of colloidal solid particles which lead to a significant decrease in the pH value. The following equation represent this reaction.
-
H+ H
+
+ +C C 3 =Ca + +C 2 +H 2O a O O
15 2 pH >8.5, (usually pH raise to be 9 or 10) B- Remediation of +alkali soils requires reducg exchangeable Na - It should be replaced by Ca - Gypsum [Ca(SO4)2. 2H2O] usually used as source of calcium. So, addition of gypsum to alkali soil, then mixed well with soil, and followed by irrigation. - gypsum slightly dissolves in water and produce calcium ions (Ca++), then calcium ions replaces exchangeable Na. As the reaction proceeds, exchangeable Na+ reduced and ESP gets lower than 15.Then, pH decreased to be lower than 8.5, and physical properties of soil improved to be suitable for plant growth.
N +C S 4 .2 H 2O =C +N 2 SO 4 a a O a a N a
The higher the CEC values the higher the amount of nutrients available to plant and reduction the amount lost by leaching. i.e., Protection of nutrients from being lost by leaching
1- Exchange between solid particles and hair roots. 2- Exchange between particles themselves.
IV - Pollution Control
Ion exchange process plays an important role in decreasing the hazardous of pollutants.
s
Hazardous of pollutants increased as they exist in mobile form in soil solution. As these pollutants attracted to negative charges exist on the surface of colloidal particles, they transformed to less mobile form, which reduces their down movement to pollute ground water and reduces their uptake by plant and introduction into food chain.
Plant nutrition
What is an essential element?
Nitrogen
These elements called nutrients Nutrients : Elements essential for plant growth (e.g., Carbon, Hydrogen, Oxygen, Nitrogen, Phosphoresces, Potassium, Calcium, Magnesium, Slushier, Iron, zinc, Manganese, Coppor, Boron, Molybdenum and chlorine). Scientists reported that, among all elements absorbed by plant and exist in their tissues, only 16 elements are reported as essential elements till now. Other elements may added to this group in future. Elements such as, Ni and Co, are called beneficial elements. May be their necessities to plant ascertain in near future.
Essential elements and the chemical forms most commonly taken up by plants.
Two elements (Ni and Co) are approaching to be added to essential elements.
Ni and Co are
Carbon, Hydrogen, & Oxygen Directly involved in photosynthesis, which accounts for most of plant growth: 6 CO2 + 12 H2O 6 O2 + 6 (CH2O) + 6 H2O Nitrogen Found in chlorophyll, nucleic acids, and amino acids. Component of protein and enzymes Phosphorus Important for plant development including: photosynthesis, respiration, cell division, and other processes Essential component of Adenosine Triphosphate (ATP), which is directly responsible for energy transfer reactions in the plant. Essential component of DNA and RNA, and phospholipids, which play critical roles in cell membranes.
s s s
s s s s
Potassium Found in ionic form in the cell, rather than incorporated in structure of organic compounds. Responsible for regulation of water usage in plants Involved in photosynthesis , drought tolerance, protein synthesis
s
Calcium Essential for cell elongation and division. Specifically required for root and leaf development Magnesium Primary component of chlorophyll and is therefore actively involved in photosynthesis. Involved in phosphate metabolism, respiration, and the activation of several enzyme systems.
Boron Essential for germination of pollen grains and growth of pollen tubes Forms sugar/borate complexes associated with the translocation of sugars, starches, N, and P.
s
Iron Serves as a catalyst in chlorophyll synthesis. Involved in many oxidation-reduction reactions during respiration and photosynthesis.
s
Manganese
Functions primarily as a part of the enzyme systems in plants. Activates several important metabolic reactions (enzymes).
Zinc Essential for promoting certain metabolic/enzymatic reactions. Necessary for the production of chlorophyll, carbohydrates, and growth hormones. Molybdenum Essential in the process of symbiotic N fixation by Rhizobia bacteria in legume root nodules. Chlorine Involved in: energy reactions in the plant Serves as a counter ion in the transport of several cations in the plant.
s
Anions (negatively charged ions) usually leach more readily than cations because they are not attracted to the predominantly negative charge of soil colloids. For example, NO3- , due to its negative charge and relatively large ionic radius, is not readily retained in the soil and is easily lost from soils by leaching. An exception to this behavior is phosphorus anions (HPO4=,H2PO4-). These anionic forms do not easily leached through the soil profile because of their specific complexing reactions with soil components.
The relationship between soil pH and the relative plant availability of nutrients.
In general; except for Mo and B, the availability of most nutrients increased as soil pH decreased to be lower than 7. P: Phosphorus Plant availability of P is generally greatest in the pH range of 5.5 6.5. When soil pH falls below 5.5, P reacts with Fe and Al to produce insoluble Fe and Al phosphates that are not readily available for plant uptake. At pH higher than 6.5, P reacts with Ca to form Ca phosphates that are relatively insoluble and have low availability to plants. K, Ca, and Mg: These nutrients are most present in soils in available form at pH higher than 6.0. Their availability to plants decreased in acid soil. They may have been partially leached out of the soil profile.
Micronutrients: In general, most micronutrients are more available in acidic than alkaline soils. As pH increases, micronutrient availability decreases. An exception to this trend is Mo and B; their availability increase as soil pH increases. Al, Fe, and Mn Toxicity: At pH values less than 5.0, solubility of Al, Fe, and Mn increase and their concentrations in soil solutions increase to be toxic to plant.
Fertilizers
Fertilizers
s s
Expressions:- Fertilizer: Any organic or inorganic material of natural or synthetic origin that added to soil to supply plant with one or more essential element. - Fertilization: The process in which nutrients are added to soil in the form of chemical fertilizers, animal manure, green manure or compost. Foliar fertilization : Application of a dilute solution contains nutrient elements to plant foliage, usually, to supplement nutrients absorbed by plant roots. Fertigation: Application of nutrients through irrigation water.
Fertilizers
s s
Fertilizers are classified into two major groups: 1- Organic fertilizers 2- Inorganic fertilizers (mineral fertilizer or chemical fertilizer) - Inorganic fertilizers classified to 2 types; - Simple (single) fertilizers: in which a fertilizer contain only one nutrient (e.g., urea) - Complete fertilizer: in which a fertilizer contain two or more nutrients.
Useful Expression Fertilizer analysis : The percentage composition of fertilizer, expressed in terms of nitrogen (N) , phosphors penta-oxide (P2O5 ) and Potassium oxide ( K2O ) - Fertilizer fixation : The process by which available plant nutrients are rendered less available or unavoidable in soil. - Fertilizer requirement : The quantity of certain nutrient needed to increase plant growth to optimum yield.
IV - Micronutrient Fertilizers Micronutrients are usually supplied in chelated form and added to plants by foliar spraying. Also, they could be supplied in mineral form. However, mineral form is less soluble. Definition: Chelating agent are organic molecules such as EDTA, EDDHA,... These compounds have the ability to make chemical bonds (co-ordinate covalent bond) with Fe, Mn, Cu, Zn. The chelates are readily soluble, even at higher pH values, which increase their suitability and high efficiency for plants. They could be added either to soil or by foliar applications. - Mineral Sources of micronutrient fertilizer: Micronutrients are usually supplied in sulphate form, such as; Ferrous sulphate, FeSO4.7H2O, Mn sulphate, Zn sulphate and Cu sulphate .. - Other micronutrients such as boron is supplied in form of Borax, and Molybdenum in form of ammonium molybdate.
2 Organic fertilizers
s
Organic fertilizers are the residues of plant and animals usually contain various macro- and micro-nutrients in an organic form and in different quantities. These fertilizers include, cow manure, chicken manure, farmyard manure, compost and green fertilizer. Usually nutrients of organic fertilizers exist in an organic form not available to plant. Organic manure should be decomposed by micro-organisms to transform nutrients to simple ions in mineral form such as, NO3, K+, Mn++,.. Available to plant. Organic fertilizers have many advantages to soil and plant, besides they provides macro- and micro-nutrients to plant.
Term paper: You can Choose any agricultural issue to speak about. Or one of the following subjects: 1- Physical weathering 2- Chemical weathering 3- Biological weathering 4- Time as soil formation factor 5- Types of Egyptian soil 6- Types of Somali soils 7- Types of Nigerian Soils 8- Types of Chad soils 9- Sedentary soil 10- Transported soil 11- Organic fertilizers 12- Compost 13- Nitrogenous fertilizers 14- Potassium fertilizers 15- Phosphate fertilizers 16- Micronutrient fertilizers 17-Chelating fertilizers 18- Foliar fertilization 19- Soil texture 20- Soil structure 21- Soil erosion 22- Desertification 23- Cation Exchange Capacity of Soil 24- Soil Buffering action 25- Soil pH 26- Soil solution 27- Role of Hydrogen ion in chemical weathering 28- Soil formation processes 29- Hydrous oxides in soil 30- Amorphous material in soil 31- Humus formation
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