Soil Acidity and Liming

Soil Acidity and Liming

1. Introduction
   1. Aqueous systems (like the soil) exhibit the property of being acid or basic depending on the relative amounts of H ⁺ and OH^- ions present.
      
      
   2. Soils in areas with high rainfall are usually acid. Basic cations are leached more readily than Al. The presence of exchangeable Al ⁺³ results in acid soils.
      
      3 = acid peat soils
      
      4,5,6 = pH range common for humid regions mineral soils
      
      7,8,9 = common pH range for arid regions soils
      
      10 and 11 = alkali mineral
   
   
2. Measuring Acidity
   
   pH measures active acidity or the H⁺ concentration of the soil solution.
   
   pH = log 1/[H⁺] where H⁺ is the concentration in moles per liter
   
   

   [H+] (moles/liter)	pH
   .001	3
   .0001	4
   .00001	5
   .000001	6
   .0000001	7

   
   
   A 10-fold change in H⁺ concentration results in a one unit change in pH.
   
   
3. Active and Potential Acidity
   
   
   1. an acid ionizes into hydrogen ions and the accompanying anion.
      
      HA (Potential Acidity) = H⁺ + A^- (Active Acidity)
      
      Total Acidity = Active + Potential Acidity
      
      
   2. In soils, active acidity is H⁺ in soil solution. Potential acidity is exchangeable Al⁺³.
      
      Most of a soils acidity is potential.
      
      Al⁺³ + 3H₂O ==> Al(OH)₃ + 3H⁺
      
      Both active and potential acidity must be measured to estimate the amount of lime needed.
   
   
4. Causes of Soil Acidity
   
   
   1. Parent Material - Rocks from which soil was formed may have been basic or acidic
   2. Rainfall - The higher the average annual rainfall the more leaching. Basic cations are removed more readily than H⁺ and Al⁺³.
   3. Native vegetation - Soils under forest are more acid than those developed under grassland.
      
      Decomposition of O.M. forms acid
      
      CO₂ forms H₂CO₃
   4. Fertilizer containing NH₄⁺
      
      Conversion of NH₄⁺ => NO₃^- produces H⁺ ions
   5. Hydrolysis of Al
      
      Al + H₂O ===> AlOH₃ + H⁺
      
      Al can come from clay structures
   
   
5. Reasons to Add Lime
   
   
   1. to neutralize toxic elements
      
      
      1. Al⁺³
         
         
         1. Reduces root growth by inhibiting cell
            
            
         2. Reduces Ca uptake
            
            
         3. Fixes soil Phosphorus
         
         
      2. Mn ²⁺ -- toxicity is a problem on red, clayey acid soils
         
         
      3. At pH 4 or less, H⁺ can damage root membranes
      
      
   2. Increases molybdenum availability. Mo is the only micronutrient that is more available at higher pH's.
      
      
   3. To Supply Ca and Mg - ( two of the secondary nutrients).
      
      
   4. Increases microorganism activity for N fixation and nitrification
      
      
   5. Increases efficiency of P fertilization. P is fixed and not available to plants at low pH's.
      
      
   6. Improves soil physical properties. (structure)
      
6. Determining lime requirements of a soil
   
   
   1. Concept of buffer capacity
      
      
      1. buffering - a resistance to change in pH. Removal of H⁺ ions from the soil solution results in their replacement by H⁺ ions (Al⁺³) from the exchange complex.
         
         
      2. The higher CEC of a soil the greater will be its buffer capacity because more reserve (potential) amount must be neutralized to change the pH. The percent OM must be taken into account as well as the pH when estimating the amount of lime needed to raise the pH.
         
         Clay soils have a high buffer capacity.
         
         Organic soils have a high buffer capacity.
         
         Sandy soils have a low buffer capacity.
         
         Example of the effect of CEC on lime requirements and buffer capacity
         
         
         
         We want to change from pH 5 to 6. We look at the curve and see that this is a change from 25 to 75% base saturation or a 50% change.
         
         How many meq of H⁺ must be neutralized if the CEC of the soil is 2?
      
      
   2. Soil testing labs use an indirect method of measuring exchangeable acidity.
      
      
      N.C. method
      
      
      add 10 cm³ soil + 10 ml water + 10 ml buffer at pH 6.6
      
      measure the pH
      
      It has been determined that each .1 decrease in pH of the solution equals 0.4 meq ac/100 cm³ of soil
      
      rapid - large numbers of soil samples can be processed.
      
      
   
   
7. How lime neutralizes acidity.
   
   H⁺ H⁺ + CaCO₃ ==> Ca²⁺ + H₂O + CO₂
   
   in solution
   
   CaCO₃ + H₂O ==> Ca²⁺ + HCO₃^- +OH ^-
   
   This can react with H⁺ ==> HOH (water) or to precipitate Al as Al(OH)₃
   
   Lime reduces the concentration of H⁺ ions and increases the concentration of OH ^- ions, and adds non acid forming cations. the material must contain an anion that combines with and neutralizes H⁺ ions and Al ions.
   
   CO₃ ............. does
   
   SO₄..............doesn't
   
   oxides .......................CaO
   
   hydroxides.................CaOH
   
   carbonates.................CaCO₃
   
   silicates .....................SiO₃^-
   
   
8. Factors influencing the quality of liming materials
   
   
   1. purity - any impurities in the lime will reduce its ability to neutralize acidity. ( sand, rocks, clay, etc. )
      
      
   2. fineness - large particles react more slowly and less completely than fine particles.
      
      

      Particle Size	Efficiency Rate (%)
      larger than 4 mesh	0
      4-8 mesh	10
      8-20 mesh	20
      20-60 mesh	60
      60-80 mesh	80
      100 mesh	100

      
      
      

      In NC for calcitic	25% through 100 mesh
      	90% through 20 mesh
      dolomitic	35% through 100 mesh

      
      
      
   3. neutralizing value - the ability to neutralize acids. expressed in terms of calcium carbonate equivalent. Calcium carbonate is the standard by which other materials are measured ( 100%) Molecular weight of CaCO₃ is 100 MgCO₃ is 84 1 molecule of each will neutralize the same amount of acid but on a weight basis it only takes 84g of MgCO₃ to do the job of 100g of CaCO₃. Neutralizing value (CCE) calcium carbonate equivalent of the pure forms of some commonly used liming materials
      
      

      	Neutralizing Value
      CaO	179
      Ca(OH)2	136
      CaMg(CO3)2	109
      CaCO3	100
      CaSiO3	86

1. Liming materials - To be considered a liming material an anion must produce OH ^- ions to react with H⁺ and Al³⁺ ions. Oxides, hydroxides, carbonates, and silicates
   
   
   1. Calcium oxide (CaO) Common names - burned lime, quicklime, unslaked lime
      
      CaCO₃ ===> CaO + CO₂
      
      Advantage is immediate reaction with the soil.
      
      Disadvantage - caustic, difficult to handle and apply
      
      Caking may occur. Through mixing is necessary
      
      
   2. Calcium hydroxide (Ca(OH)₂)
      
      common names -- slaked, hydrated, builders lime
      
      CaO + H₂0 ===> Ca(OH)₂
      
      Advantage - quick reaction with the soil
      
      Disadvantage - difficult and unpleasant to handle
      
      
   3. Calcitic limestone (CaCO₃)
      
      Dolomitic limestone (CaMg(CO₃)₂)
      
      Mined from deposits. Quality depends on amount of impurities such as clay. Good handling properties. Reaction time several months.
      
      
   4. Marl (CaCO₃)
      
      Unconsolidated deposits of CaCO₃. Usually contaminated with clay. Low in Mg.
      
      
   5. Slags (CaSiO₃)
      
      byproduct of furnaces used for making iron, steel and elemental P.
      
      
   6. Placement of lime - Thorough mixing of lime throughout the zone of root growth is ideal.
      
      
      1. Particles of lime do not move in the soil.
      2. Application - Spread half of lime and plow down. Spread other half and disk. On established sods, lime must be topdressed. Reaction is slower and less complete. * Add smaller amounts more often.
      
      
   7. Factors determining the selection of a liming program.
      
      
      1. Lime requirements of crop to be grown. Plants differ in pH requirements.
         
         acid - blueberries, cranberies, azaleas and camellias
         
         neutral alkaline - Sweet clover, alfalfa, sugar beets.
         
         Field crops in N.C. 5.8 - 6.2 is best.
         
         Turf - 6.5 except centipede 5.5
         
         
      2. Texture and O.M. content affects amount of lime required to change pH and frequency of application. Overliming coarse textured soils is a possibility.
         
         
      3. Time and frequency of liming - use soil test. Depends on texture and organic matter content. Nitrogen fertilization and crop removal. Take soil samples at least every 3-5 years.
         
         
      4. Liming material to be used.
         
         Purity, fineness, calcium carbonate equivalent
         
         Fluid Lime
         
         
         1. good distribution pattern, no dust
            
            
         2. finely divided - reacts quickly with soil
            
            
         3. 500-1000 pounds per acre applied at one time. Reg. annual applications.
            
            
         4. 2 to 4 times more expensive
   
   
2. Acidulating the soil
   
   
   • arid western regions of the country
   • overlimed soils
   • further acidification of soils for growth of plants such as potatoes, azaleas, rhododendrons or camellias.
   
   elemental sulfur, sulfuric acid, aluminum sulfate, iron sulfate and ammonium sulfate.
   
   
   1. Elemental sulfur - pound for pound is most effective. Converted to sulfuric acid in warm moist soils by bacteria.
   2. Sulfuric acid H₂SO₄
   3. Aluminum sulfate - commonly used by Horticulturists for acidulating soil for azaleas, camellias, rhododendrons, etc.
   4. Iron sulfate ( FeSO₄) - reacts similar to aluminum sulfate.