Organic Matter 1. Aluminosilcates are composed of two fundamental units: silica tetrahedra and aluminum octahedra to form sheet-like structures. 2. Cation substitutions can take place in either the tetrahedral sheet or the octahedral sheet which result in negative charge on the mineral. 3. The total number of negative sites on clay minerals is represented by the Cation Exchange Capacity (CEC). 4. Positively charged cations are attracted to the negative sites on clay minerals which can function as storage for important plant-essential nutrients. 5. Preference for cations at mineral surfaces is dictated by charge, concentration in solution and size of the cation. Flocculation means to bring particles together Dispersion pushes particles apart. - charge Na+ Al3+ Al3+Na+ Na+ 3+ Na+ Al Na+ Na+ Na+ Na+ Na + - charge - charge 2000 B.C. Small, higher-charged cations tend to flocculate clay particles. Ca2+, Mg2+, Al3+ Large cations with low charge tend to disperse clay particles Na+, K+ Iron oxides originate from iron-bearing primary or secondary minerals. Reduced iron (Fe2+) occurs in low-oxygen environments and results in a greyish color. Oxidized iron (Fe3+) occurs in high oxygen environments and results in orange-red colors. Water restricts diffusion of oxygen in soils Grey colors interspersed with orange-red colors often indicates the presence of water tables in soils. Iron and Aluminum Oxides Can possess negative, positive, zero charge Potential interaction with cations and anions Cl-, F-, Br-, SO42-, NO3-, CO32-, PO43Anion Exchange Silicate Clays vs. Al/Fe oxides Silicate clays possess negative charge due to isomorphous substitution during the formation of the mineral. Cation Exchange Iron and aluminum oxides are products of weathering and can possess negative positive or zero charge. Charge derives from Interaction with hydrogen ions in solution. Cation or Anion Exchange Soil Organic Matter and Organic Colloids Organic matter plant debris or litter in various stages of decomposition and includes the living organisms in the soil Soil Organic Matter Accumulation of partially disintegrated and decomposed plant and animal residues as well as living biomass . Decomposition principally by soil microorganisms Transitory soil constituent (hours to 100s of years) Requires continual addition to maintain O.M. levels. 1 – 5% (by weight) in a typical, well-drained mineral soil Soil Organic Matter Aids in soil aggregation, structure Increases water-holding capacity/porosity Can increase infiltration rates. Principal source of essential plant nutrients Energy source for soil microorganisms Categories Soil Organic Matter: Natural C-containing organic materials living or dead Microbial Biomass: It is the living population of soil microrganisms. Litter: It comprises the dead plant and animal debris on the soil surface. Macroorganic Matter: Organic fragments from any source which are > 250µm (generally less decomposed than humus). Humus: Material remaining in soils after decompostion of macroorganic matter. Organic Carbon: The carbon content is commonly used to characterize the amount of organic matter in soils. Organic matter = 1.724 x percent organic carbon or, organic matter is 58% organic carbon Composition Plant Materials Carbon (42%) Hydrogen (8%) Oxygen (42%) Nitrogen, Sulfur, Phosphorus, Potassium Composition plants compounds elements Soils and Global Carbon Carbon Soils contain more that 4x more Carbon than all vegetation combined. Amounts 2400 pentagrams (1015 g) in soil 700 pentagrams as soil carbonates Storage of earth carbon Decomposition Compounds Sugars, starches Crude proteins Hemicellulose Cellulose Fats, waxes Lignins, phenols Rapid Decomposition Slow Decomposition Decomposition The biochemical breakdown of mineral and organic materials. Majority of breakdown results in Carbon dioxide, water, energy and heat Essential elements (N, P, S) are released This is called “mineralization” Some of the substrate carbon is incorporated into the cells of microorganisms: called “immobilization” Highly resistant compounds are formed which remain in the soil for long periods: “humification” Humus amorphous, colloidal, organic substances (possessing no plant cellular organization) Highly resistant to breakdown Can be highly reactive due to carbon content, surface area, and charge Humic Substances a series of high-molecular-weight amorphous compounds Fulvic Acids decay products of higher plants and microbial residue. Humic Acids products of fulvic acids and other decay products Impacts of SOM on Soil Chemical Properties Cation Exchange Soil Acidity Absorption of Organic Compounds Soil Organic Matter, Acidity, and Reactivity Acid Any substance which increases the hydrogen ion concentration in solution. + H Common Acids Hydrochloric Acid Sulfuric Acid Nitric Acid Carbonic Acid Acetic Acid Ammonium HCl H2SO4 HNO3 H2CO3 HC2H3O2 NH4+ Strong Acids HCl H+ + Cl- HNO3 H+ + NO3- H2SO4 H+ + HSO4Reaction goes to completion (complete dissociation) Weak Acids Ammonium Carbonic Acid Acetic Acid NH4+ H2CO3 HC2H3O2 NH4+ NH3 + H+ (residual NH4+) H2CO3 HCO3- + H+ (residual H2CO3) HC2H3O2 C2H3O2- + H+ (residual HC2H3O2) Incomplete dissociation Incomplete Dissociation NH4+ NH3 + H+ (residual NH4+) H2CO3 HCO3- + H+ (residual H2CO3) HC2H3O2 C2H3O2- + H+ (residual HC2H3O2) NH4+ NH3 + H+ In pure water, the amount of dissociation is known Incomplete Dissociation NH4+ NH3 + H+ In pure water, the amount of dissociation is known High amounts of NH3 and/or H+ inhibit dissociation The reaction is inhibited in acid solutions (high (H+)) pH A measure of the amount of Hydrogen ions in water - Log (H+) Low pH = High amount of Hydrogen ions in water High pH = Low amount of Hydrogen ions in water Low pH = High amount of Hydrogen ions (acidic) High pH = Low amount of Hydrogen ions (basic) Scale: 1 - 14 Battery Acid = < 1 Coca Cola = 2.8 Vinegar = 3.0 Orange Juice = 4.2 Beer = 4.3 Pure Rain = 5.6 Incomplete Dissociation Weak Acid NH4+ NH3 + H+ In pure water, the amount of dissociation is known High amounts of NH3 and/or H+ inhibit dissociation The reaction is inhibited in acid solutions (low pH) Relevance to Soil Organic Matter Organic Matter Accumulation of partially disintegrated and Decomposed Plant and animal residues. Carbon (42%) Hydrogen (8%) Oxygen (42%) Nitrogen, Sulfur, Phosphorus Humus: amorphous, colloidal, organic substances 58% carbon Carbon Oxygen Hydrogen Cation Exchange COOH OH carboxylic Enolic/phenolic Acid functional groups Carbon Hydrogen Oxygen COO- + H+ COOH O- + H + OH Both are weak acids (incomplete dissociation) H+ + Cl- HCl NH4+ NH3 + H+ (residual NH4+)) COOH COO- + H+ Soil solution OH O- + H + The dissociation of weak acids is inhibited by H+ in solution Low pH = lots of H+ = less dissociation = low charge High pH = little H+ = more dissociation = high charge Dissociation of Hydrogen Soil solution COOH COO- + H+ organic strand -C-C-C-C- OH O- + H+ COOH OH COO- + H+ O- + H + Both are weak acids (incomplete dissociation) The dissociation is inhibited by H+ in solution Low pH = lots of H+ = less dissociation = low charge High pH = little H+ = more dissociation = high charge Cation Adsorption COOH COO- + K+ COO- + H+ COO---K Adsorbed cation Cation Exchange COOH O- Soil Solution Ca2+ COO- Mg2+ Na+ COOCOO- K+ K+ Na+ OH + O- Na COO- Organic strand Functional Groups COOH COOOH O- K+ K+ + O- Na O- Mg2+ COO- H+ H+ Mg2+ Na+ H+ Na+ K+ Mg2+ H+ Na+ Na+ Na+ - - - - K+ K+ Na+ Cations and Organic Matter K+ Mg2+ Na+ K+ K+ CEC = 100 – 500 cmol/Kg Mg2+ Mg2+ K+ K+ Na+ K+ Na+ Na+ Mg2+ Mg2+ Kaolinite 2-5 cmol/kg Vermiculite 100-180 cmol/kg Cation Exchange Mineral organic Si Al Si Ca2+, Mg2+, Zn2+, Mn2+, K+, NH4+, Na+, H+, Mn2+ Total Cation Exchange Capacity Mineral Total CEC = Si Al Si pH-Dependent Organic + Mineral Colloids derive charge from substitution Of lower-charged cations for higher charged cations In the crystal matrix during mineral formation. The Result is permanent negative charge. Organic colloids derive their charge from dissociation of hydrogen ions from acidic functional groups on organic matter/humus. The result is pH-dependent charge Mineral Colloids – 0 – 180 cmol/kg Organic Colloids – 100 – 500 cmol/kg Reactivity of Soil Horizons Contribution to fertility.