1. Soil Acidity Effect of pH and Aluminum on Corn Yield in PA

2. Soil Acidity Active Acidity Potential Acidity

3. Soil Acidity Ca ++ Mg ++ K+K+ H+H+ Al +++ NH 4 + Ca ++ Al +++ Mg ++ Al +++ H+H+ K+K+ H+H+ H+H+ H+H+ H+H+ H+H+ H+H+ Quantity: Potential Acidity Intensity: Active Acidity pH Buffering

4. Soil Acidity Soil Acidity Buffering –Soils tend to buffer pH High clay and/or organic matter greater buffering Low clay and/or organic matter lower buffering pH Acidity (Limestone applied) Clay Loam CEC = 25 meq/100g Silt Loam CEC = 15 meq/100g Sandy Loam CEC = 10 meq/100g Sand CEC = 5 meq/100g Textbook Fig. 3.5

5. Soil Acidity and Liming

6. Soil Acidity Determining exchangeable acidity –1 eq. Base for each 1 eq. of Acidity –Titration Add increasing amount of base measure pH change Added Base Soil pH

7. Soil Acidity Determining exchangeable acidity –Buffer pH Add a pH buffer solution and measure pH change Known relationship between pH change and change in acidity Common pH buffers –SMP (used in PA) »Triethanolamine »Paranitrophenol »Potassium chromate »pH 7.5 –Adams-Evans –Mehlich –Woodruff

8. Soil Acidity Determining exchangeable acidity –Buffer pH Add a pH buffer solution and measure pH change Known relationship between pH change and change in acidity Common pH buffers –SMP (used in PA) »Triethanolamine »Paranitrophenol »Potassium chromate »pH 7.5 –Adams-Evans –Mehlich - Many states including PA going to this –Woodruff NOTES

9. Soil pH & Buffer pH H+H+ H+H+ H+H+ H+H+ H+H+ H+H+ H+H+ H+H+ H+H+ H+H+ H+H+ H+H+ H+H+ H+H+ H+H+ H+H+ H+H+ H+H+ H+H+ H+H+ H+H+ H+H+ H+H+ H+H+ H+H+ H+H+ H+H+ H+H+ H+H+ H+H+ H+H+ H+H+ H+H+ Soil pH Buffer pH Water SMP Buffer

10. SMP Buffer Curve

11. SMP Buffer Relationship Buffer pHExch. Acidity (meq/100g) Lime Rec. For pH 6.5 (lb/A) 7.020 6.832000 6.643000 6.475000 6.298000 6.01110000 5.81412000 5.61614000 5.41916000 aasl.psu.edu

12. Soil Acidity and Liming Determining Lime requirement –Exchangeable Acidity 1 meq. Base/100g for each 1 meq. of Acidity/100g How many pounds of lime do we need per acre?

13. Soil Acidity and Liming Determining Lime requirement –Desired pH Acid sensitive crops pH 7.0 Most crops and soils pH 6.5 Highly weathered soils pH 5.5 Acid loving crops 5.5 - 6.0

14. Soil Acidity and Liming Determining Lime requirement –Based on target pH and Exchangeable acidity Formulas used by PSU AASL For pH 7.0 84500 – (12180 x SMP Buffer pH) = CaCO 3 /A For pH 6.5 71240 – (10280 x SMP Buffer pH) = CaCO 3 /A For pH 6.0 57840 – (8340 x SMP Buffer pH) = CaCO 3 /A

15. Soil Acidity and Liming Determining Lime requirement –Rules of thumb For pH 7.0 Exch. Acidity (meq/100g) X 1000 = CaCO 3 /A For pH 6.5 Exch. Acidity (meq/100g) X 840 = CaCO 3 /A For pH 6.0 Exch. Acidity (meq/100g) X 750 = CaCO 3 /A

16. Soil Acidity and Liming Liming Materials –Material that will neutralize soil acidity Calcium Oxide (CaO) –Lime, burnt lime, quick lime Calcium Hydroxide (Ca(OH) 2 ) –Hydrated lime, slaked lime Calcium Carbonate (CaCO 3 ) –Calcitic limestone Calcium/Magnesium Carbonate (Ca,MgCO 3 ) –Dolomitic limestone

17. Soil Acidity and Liming For each equivalent of acidity we need to apply 1 equivalent of liming material Chemical neutralizing ability of liming materials –Equivalents of OH - produced by the reaction of the liming material. Ca(OH) 2 → Ca 2+ + 2 OH - CaCO 3 + H 2 O → Ca 2+ + 2 OH - + CO 2 CaO + H 2 O → Ca 2+ + 2 OH - CaSiO 3 + H 2 O → Ca 2+ + HSiO 3 - + OH - CaSO 4 → Ca 2+ + SO 4 2-

18. Soil Acidity and Liming Soil Liming Reaction Al 3+ H+H+ + Ca 2+ + CO 3 2- Ca 2+ + H + + Al 3+ + CO 3 2- CO 2 2H 2 O + + 2OH - H2OH2O + H + + Al 3+ + H 2 O + Al(OH) 3 CaCO 3 → Ca 2+ + CO 3 2- Exchange Neutralization Acid Soil Neutral Soil

19. Soil Acidity and Liming Liming material quality Calcium Carbonate Equivalent (CCE) –Neutralizing value of any liming material compared to pure calcium carbonate

20. Soil Acidity and Liming Calcium Carbonate Equivalent (CCE) –1 Eq. of CaCO 3 = 1 Eq. of any liming material

21. Soil Acidity and Liming Calcium Carbonate Equivalent –Example: MgCO 3 MgCO 3 = 84 g/mole or 42 g/ eq. CaCO 3 = 100 g/mole or 50 g/ eq.

22. Soil Acidity and Liming Calcium Carbonate Equivalent (CCE) Material% CCE CaCO 3 100 MgCO 3 119 (Ca,Mg)CO 3 109 CaO179 Ca(OH) 2 136 CaSiO 3 86 Common Limestones80 - 100

23. Soil Acidity and Liming Soil test recommendations are made as lb CCE/A Adjust if CCE is different from 100% –Example: Recommendation = 2000 lb CCE/A Hydrated Lime Ca(OH) 2 CCE = 136% Required amount of liming material = 100 x Rec. CCE/A % CCE of Material

24. Soil Acidity and Liming Real World –Not usually dealing with pure materials, so we can't always calculate the CCE –Measure CCE in lab – Required in most states Titration with standard acid –CCE is provide on the label for all liming materials sold in PA –Be careful calculating CCE on unknown materials

25. Estimating Neutralizing Value of Liming Materials - Be very careful - Ca x 2.5 = CaCO 3 Mg x 3.5 = MgCO 3 MgCO 3 x 1.19 = CaCO 3 MgO x 2.5 = CaCO 3 CaO x 1.79 = CaCO 3 Unknown material analysis given as 23% Ca You have to know the form of the Ca or Mg to use these conversions!

26. Estimating Neutralizing Value of Liming Materials - Be very careful - If you don’t know what the material is made of then you need to measure the CCE directly! Cost ~ $10-15

27. Soil Acidity and Liming Calcium Oxide Equivalent (COE) –Neutralizing value of any liming material compared to pure calcium Oxide –1 Eq. of CaO = 1 Eq. of any liming material –1 Eq. wt. of CaO = 1 Eq. wt. of any liming material COE = eq. wt. CaO/ eq. wt. Liming material COE = 28/ eq. wt. Liming material

28. Soil Acidity and Liming Soil test recommendations may be made as lb COE/A Adjust if COE is different from 100% Required amount of liming material = 100 x Rec. COE/A % COE of Material

29. Soil Acidity and Liming Physical fineness of liming materials –Fineness determines speed of reaction –The finer limestone is ground the faster it will react –Fineness given as % passing specific screen mesh sizes

30. Soil Acidity and Liming 7 6 5 4 pH 0 12 24 36 Reaction Time (Months) 100 Mesh 60-80 Mesh 40-60 Mesh 20-40 Mesh 8-20 Mesh No Lime Equal neutralizing value applied Effect of aglime fineness on speed of reaction

31. Soil Acidity and Liming Physical fineness of liming materials –Practical Limits to fineness –Larger than 20 mesh – not effective –Smaller than 100 mesh – little added benefit

32. Soil Acidity and Liming 7 6 5 pH 0 1 3 5 10 Tons per acre 100 M 60-80 M 40-50 M 30-40 M 20-30 M 8-20 M Effect of limestone fineness on soil pH change

33. Soil Acidity and Liming 200 100 60 40 20 8 0 5 20 50 80 99.9 99 95 Sieve Size (Mesh) Cum. % Passing Particle Size Distribution from Grinding

34. Soil Acidity and Liming Aglime Fineness –Pulverized Limestone Normal ground Limestone –Granular Limestone Coarser ground limestone Easy spreading for homeowners Slower to react

35. Fine Sized Materials Medium Sized Materials 95% - 20 mesh sieve 60% - 60 mesh sieve 50% - 100 mesh sieve Coarse sized materials - all liming materials failing to meet the above fineness criteria Aglime Fineness Fineness definitions for PA 90% - 20 mesh sieve 50% - 60 mesh sieve 30% - 100 mesh sieve

36. Aglime Quality Acid-Base Chemistry and Fineness CaCO 3 + H 2 O  Ca 2+ + H 2 CO 3 + 2OH - 2OH - + 2H +  2H 2 O For a given amount of acidity an equivalent amount of base (liming material) will be required regardless if it is ground very fine.

37. Aglime Quality Acid-Base Chemistry in soils 1 meq/100g acidity in the soil will require 1 meq/100g of CaCO 3 to neutralize it. 1 meq CaCO 3 /100g soil = 1000 lb CaCO 3 /A

38. Soil Acidity and Liming Aglime Fineness –No matter how fine you grind limestone you cannot increase the chemical neutralizing ability –Finer the better, because it will react faster, but there are practical limitations –Distribution in “Fine Size” Limestone – usually adequate for practical liming for field crops –Little difference between calcite and dolomite

39. Soil Acidity and Liming 5 4 3 1 Relative Lime Requirement 0 20 40 60 80 100 % Passing 60 Mesh 2 Dolomitic Calcitic 2-4 yr Effect of type of limestone and rate required for equal crop response

40. Soil Acidity and Liming Pellet Lime –Finely ground limestone –Glued together into water soluble pellets –Advantage: Handling, spreading, speed of reaction –Disadvantage: Cost 100-200 mesh

41. Soil Acidity and Liming Fluid Lime –Finely ground limestone –Suspended in water with clay –Approx. 1000 lb CCE/ton material –Advantage: Spreading, speed of reaction –Disadvantage: Cost

42. Less than recommended very fine limestone applied compared to normal liming program 7 6 5 4 pH 0 3 6 9 Reaction Time (years) 3

43. Less than recommended very fine limestone applied annually but similar rate over time. 7 6 5 4 pH 0 3 6 9 Reaction Time (years)

44. Soil Acidity and Liming -0.6 -0.4 -0.2 0 0.2 0.4 0.6 0.8 Start1994199519961997 Change in pH Pellet Lime @ 500lb/A/yr Pulverized Lime @ 8000 lb/A Effect of Pellet Lime on Soil pH

45. Soil Acidity and Liming Calcium and Magesium –Normal liming practices will also supply required calcium and magnesium At normal rates usually adequate Ca will be supplied for most crops Magnesium will depend on the type of limestone used –If Mg is required use a Mg containing limestone (dolomitic) –Mg recommendations »pounds Mg/A »% Mg in recommended limestone

46. Calcium and Magnesium Management Recommendations –Maintain optimum pH –Maintain at least optimum levels of Mg (60 ppm) and K (100 ppm) –Don’t worry about ratios until they are way out of balance eg. Mg:Ca >1, K:Mg>1 Rare

47. By-product Liming Materials Quality –Liming value –Undesirable components

48. Example: Liming Value Material sold in western PA for $2/ton CCE = 5.38% For 1 ton of neutralizing value: 2000 X 100 ÷ 5.38 = 37,174 lbs. or 18.6 tons ($37.20) Fineness: Through 20 Mesh = 98.8% (90%) Through 60 Mesh = 78.2 % (60%) Through 100 Mesh = 63.2% (50%)

49. Gypsum CaSO 4 Excellent source of Ca and S –33% Ca & 27% S No neutralizing value Not a liming material

50. Limestone vs Gypsum Limestone changes pH  Gypsum doesn’t Both are good sources of Ca –Lime to recommended pH... no need for additional Ca for the soil or for agronomic crops in PA –High pH but low calcium soils (Sodic Soils) use gypsum as a source of Ca for the soil and the crop (Western US) Improves physical properties  Relieves chemical compaction –Low pH, acid loving crops or highly weathered soils, use gypsum as a source of Ca for the soil and the crop (Tropics) Minimal lime to reduce Al toxicity

51. Byproduct Materials Undesirable components Should be registered (PDA) Must be approved for land application by DEP –May limit lifetime application Problem with unregistered materials and materials from out of state –May be little or no checking of quality Determine the source –Dust, screenings –Stainless steel slag Ask what contaminants might be present If in doubt... get it analyzed OR don’t use it

52. Example: Undesirable components - Metals in Aglime

53. Other Materials Biosolids and Water Treatment Sludges –Often have significant neutralizing value –Must be clean –Must be registered if sold as liming materials

54. Other Materials Organic Calcium Compounds Promesol 30, Liquid Lime –Trihydroxy glutaric acid 25% Ca –1 gallon = 500-750 lb CCE? Liqui-Til –Trihydroxy glutaric acid –Neutralizes pH in alkaline soil? KK Organic Soil Builder –Neutralizes both acidic and alkaline soils? Liqui-Cal –8% Ca –1 gallon = 500 lb CaCO 3 ? Liquid Calcium –1 gallon = Ca in 500 lb CaCO 3 ? –Suggest it is a lime substitute Golden Cal –Glucoheptomic acid –1 gallon = 500 lb CCE? pH Plus –1 gallon = 500-750 lb CCE?

55. Other Materials Remember: 1 Eq. of base is required to neutralize 1 Eq. of acid Watch out for materials that contain Ca with unwritten or suggestive claims for liming value

56. Soil Acidity and Liming Limestone Application –Apply limestone far enough ahead of time to be effective –Spread limestone uniformly Spinner spreaders Boom spreaders Damp lime Dust –Spit high rates of limestone (>4 ton/A) –Time of year is not too critical Consider soil quality issues – compaction –Mix limestone as much as practical Adjust for depth of mixing - 6 2/3 in. standard depth No till – Correct pH before going to no-till

57. Soil Acidity and Liming Time (years) Soil pH vs No-Till With 6000 lbs/A of Lime Applied Every 3rd Year