BIOCHEMISTRY LECTURE MODULE LECTURES 001

Undergraduate Lecture notes

1. welcome

2. Topics Ca, Mg & S fertilizers Micronutrient fertilizers Types of fertilizer mixtures and grades their advantages and disadvantages E. Kiranmai NAM-12-02

3. Calcium The calcium concentration of the earth’s crust is about 3.20 %, it may be as low as 0.015 % in humid region to as high as 5% in arid region . High calcium content in arid regions could be due to low rainfall and hence little leaching . The major sources of calcium are the weathered products of rocks and minerals containing calcium

4. Mineral Chemical formula Total CaO (%) 1. Calcite CaCO 3 56.0 2. Apatite Ca 10 (PO 4 ) 6 50.0 – 53.2 3. Dolomite CaCO 3 .MgCO 3 33.2 4. Gypsum CaSO 4 .2H2O 32.2 primary minerals like Augite (18.7 %), Hornblende (4.6%), Anorthite (10.0 – 20.0 %), Epidote (22.0-25.0%) etc., are the sources of calcium in the soil.

5. Forms of calcium in soils : Calcium is generally the dominant cation in normal cultivated soils. The calcareous soils have higher amount of Ca than acid soils. Mineral particles : Calcium is mostly present as primary minerals such as basic plagioclase like anorthite , and basic rocks like basalt, gabbro. They all release Ca on weathering. Calcium carbonate : Calcite mineral is very common. The nodular form of calcium carbonate and amorphous calcium carbonate exist. Simple salt : calcium is present in many simple salts such as calcium chloride , calcium sulphate, calcium nitrate and calcium bicarbonate. Exchangeable calcium : Of all the cations on the exchange complex of soils Ca²⁺ is the most dominant cation .

6. Factors Affecting Ca Availability : Soil pH: usually soils with a higher pH level contain more available Ca Presence of competing ions - calcium competes with other positively charged ions, such as Na ⁺ , K ⁺ , Mg ⁺² . Applying too much of these (+) vely charged ions might decrease calcium uptake by plants. Sodium ions can replace the adsorbed calcium, damage soil structure and decreases Ca availability.

7. Soil CEC : Lower CEC soils hold less Ca, and high CEC soils hold more. Sub-soil or parent material : Soils derived from limestone, marl , or other high Ca minerals will tend to have high Ca levels, while those derived from shale or sandstone will tend to have lower levels.

8. Magnesium : Magnesium is absorbed by plants from the soil solution as Mg+2. It constitutes 1.93 % of the earth’s crust ranging from 0.1 % in coarse sandy soils of humid region to 4 % in fine textured soils of arid and semi arid regions. Mg in soil originates from weathering of biotite , dolomite, hornblende, olivine, epsomite (MgSO4. 7 H2O) and serpentine . Also found in secondary clay minerals like chlorite, illite , montmorillonite and vermiculite; excess Mg may be seen in soils developed from serpentine bed rock. If large quantities of magnesium are added to montmorillonite , it may convert to vermiculite

9. Sources Of Mg In Soils: The Mg content of soils depend upon: Parent material. The degree of leaching of soil. The texture of the soil. The fertilizer practices adopted. Generally , minerals like biotite , dolomite ,chlorite, serpentite , olivine and secondary clay minerals rich in Mg are the sources of Mg in the soils.

10. Fate of released Mg : On decomposition of primary minerals, Mg is released into soil which may then be 1) Lost in the percolating water. 2) Absorbed by living organisms. 3) Adsorbed by surrounding clay colloids. 4) Reprecipitated as secondary mineral in arid regions

11. Factors affecting the availability of Mg Amount of exchangeable Mg+2 : Soils are deficient in Mg when they contain less than 25 to 50 ppm of exchangeable Mg+2. Soil pH : Nutritional problems of Mg⁺²will arise in strongly acid soils with Al³⁺ saturation of 65 to 70 %. The availability of Mg²⁺ can also be adversely affected by high H⁺ activity in strongly acid soils. Degree of Mg saturation : The more the degree of saturation the greater is its availability. When exchangeable magnesium is more than 45 %, it is toxic to plants. Magnesium availability is high when its saturation is 10 – 20 % on the exchange complex. Normally, the exchangeable magnesium accounts for 4 to 20 % of CEC. Magnesium saturation should not be less than 10 %.

12. Nature of other exchangeable ions : Plant deficiencies of Mg can occur in soils with wide Ca / Mg ratio. Ideally it should not be greater than 7:1. High levels of exchangeable K⁺ can interfere with Mg uptake. K / Mg ratio should be less than 5:1 for field crops, 3:1 for vegetables and sugar beet, 2 : 1 for fruit and green house crops. NH 4 ⁺ also interferes with Mg nutrition. Removal by crop : Legumes exhaust more Mg than non legumes. Additions through fertilizers, manures and rains : FYM and oil cakes are rich source of Mg. Basic slag contains 3 – 4% of magnesium. Serpentines contain 26 %.

13. Sulphur : The earth’s crust contains about 0.06 % sulphur . It is mostly present as sulphides , sulfates and in organic combinations with C and N. More than 95% of total S in soil is present in organic matter under temperate conditions . The initial source of all S is the sulphide contained in plutonic rocks. Through weathering the sulfides are released. Another source of S is the atmosphere. Owing to industrial activity or through combustion of fuel, SO 2 is produced which is brought down by rain .

14. Forms of sulphur in soils : Easily soluble sulphate : Sulphur is normally taken up by plants as the SO 4 ¯² ion . In sulphur deficient soils the amount of readily soluble SO 4 ¯² is frequently between 5 and 10 ppm. Sandy S deficient soils often contain less than 5 ppm. SO 4 ¯² when associated with monovalents like Na+ are more prone for leaching. Medium losses when bound to divalent like Ca²⁺ or Mg²⁺ and minimum losses when bound to Al⁺³or Fe³⁺. Adsorbed sulphate : Adsorbed sulphate is an important fraction in soils containing large amounts of hydrous oxides of iron and aluminium like in Oxisols and Ultisols . Adsorbed sulphate can account for upto 1/3rd of total sulphur . Sulfate coprecipitated with calcium carbonate : It is an important fraction in calcareous soils.

15. Sulfides : Under anaerobic conditions in water logged soils, there may be accumulation of H2S formed by the decay of organic matter. Also, SO4 = present in the soil serves as an electron acceptor for sulphate reducing bacteria and it is reduced to H2S. This reduction takes place at a redox potential of less than -150 mV and at a pH range of 6.5 to 8.5 Elemental sulphur : It is an intermediate product formed during oxidation of sulfides by chemical processes Organic form : Most of the sulphur in surface horizons of well drained agricultural soils of humid, temperate, semi arid and sub tropical regions is present in the organic form. It accounts for more than 90 %.

16. Micronutrients Cl , B, Fe, Mn , Zn, Cu, Mo, Co, Ni Sources : The main source of micronutrients in soil is the parent material . The micronutrient content of the soil entirely depends on the rocks from which the parent material is derived; soil forming processes, additions and removals. Cobalt, Nickel and copper are preferentially attached to more basic rocks. Zinc has a greater tendency to be associated with sulphides .

17. Sources of micronutrients and the forms of micronutrients in soil solution Major sources Total content (ppm) Forms is soil solutions Zinc Sphalerite -( ZnS ) Smithsonite - ZnCO 3 7 to 1000 Zn² ⁺ , Zn (OH)¯ Copper Chalcocite - Cu 2 S Covellite - CuS Malachite - Cu 2 (OH) 2 CO 3 Azurite - Cu 3 (OH) 2 (CO 3 ) 2 1.8 to 960 Cu² ⁺ , Cu (OH) ⁺ Iron Haematite - Fe 2 O 3 Goethite - FeOOH Magnetite - Fe 3 O 4 Pyrite - FeS 2 Olivine - (Mg Fe) 2 SiO 4 4000 to 27300 Fe² ⁺ , F(OH) ⁺ , Fe (OH) 2

18. Manganese Pyrolusite - MnO 2 Manganite - MnO OH 37 to 115000 Mn² ⁺ Boron Borax - Na 2 B 4 O 7 . 10 H 2 O Tourmaline – Na (Mg Fe) 3 Al 6 (BO 3 ) 3 Si 6 O 18 (OH) 4 2.8 – 630 H2BO³¯, HBO 3²¯ , BO 3 ³¯ Molybdenum Molybdenite - MoS 2 Wulfenite - PbMoO 4 Powellite - CaMoO 4 Traces to 12 MO O 4 ¯², HMO O 4 ¯ Chlorine Murate of potash - ( KCl ) Sodium chloride - ( NaCl ) 20 to 1000 Cl ¯

19. Predisposing factors for occurrence of micronutrient deficiencies in soil and plants Parent material : The soils whose parent material originally contain low amounts of micronutrients are most likely to show micronutrient deficiency under leaching and intensive cropping. Soil pH : Acid soil conditions are most conducive for Mo deficiency. Similarly, high pH soils such as sodic soils show Zn, Fe, Mn and Cu deficiency. Over liming of acid soils also causes deficiency of micronutrient cations . In acid sulfate soils micronutrient toxicity limits crop growth. Land leveling and shaping : Land leveling and shaping removes the fertile top soil in which micronutrients are concentrated. High yielding varieties : HYV require more nutrients depleting the nutrients from soil causing their deficiencies.

20. Fertilizer Mixtures (FM) When two or more fertilizers are mixed together to supply two or three major elements i.e. N , P 2 O 5 and K 2 O is known as fertilizer mixture or Mixed fertilizer. ( Or) A mixture of two more straight fertilizer materials is referred to as fertilizer mixture. Sometimes , complex utilizes containing two plant nutrients are also used in formulating fertilizer mixtures.

21. Types of fertilizer mixtures : two types Open formula fertilizer mixtures: The formulae of such fertilizers in terms of kinds and quantity of the ingredients mixed are disclosed by the manufacturers. Closed formula fertilizer mixtures: The ingredients of straight fertilizers used in such mixtures are not disclosed by the manufacturers.

22. Materials used in fertilizer mixtures : Different materials go in to production of mixed fertilizers . In accordance with their principle function in the mixture, the materials can be grouped into: Suppliers of plant materials : These are the straight fertilizers added to supply the plant nutrients mentioned in the grade, thus, are the primary materials most essential for preparing mixed fertilizers. Conditioners: These are the organic substances which prepare the fertilizer mixture in good drilling condition and reduce caking. E.g.: Tobacco stems, Peat, Groundnut hulls and paddy hulls (Husks), bone meal, oilcakes, paddy husk Peat soil Paddy husk

23. Neutralizers of residual acidity : The substances used to neutralize the residual effects are known as neutralizers. For example, if the nitrogenous fertilizers used are acidic in nature like Ammonium Sulphate, Urea, a basic material like lime stone is added to counteract the acidity. Filler : Filler is the make – weight material added to a fertilizer mixture. It is added to make up the differences between the weight of the added fertilizers required to supply the plant nutrients and the desired quantity of fertilizer mixture, such as sand, soil, ground coal ashes , sawdust and other waste products. Coal powder Sand

24. Fertilizer grade : An expression indicating the % of plant nutrient in a fertilizer mixture is termed as fertilizer grade Fertilizer ratio : the relative proportion of major plant nutrients in the mixed fertilizer taking ‘N’ as one , called as fertilizer ratio. For example, in a fertilizer mixture of 6:12:6 grades, the fertilizer ratio is 1:2:1.

25. Advantages: The balanced fertilizer mixture suited to crop and soil can be supplied, All the required nutrients can be supplied at one time by the application of fertilizers mixture and thus, time and labourers are saved. Storage and handling costs are reduced. Micro nutrients can be incorporated. Mixtures have better physical condition and are easier for application. Residual acidity can be neutralized by using neutralizers in mixture.

26. Disadvantages: The cost of plant nutrients is higher than straight fertilizers . All only one nutrient is required by the crop, the fertilizer mixtures are not useful and sometimes farmers may add nutrients in excess or in limited quantity.

27. Research articles

28. Effect of Potassium and Calcium Application on Yield, Yield Components and Qualitative Characteristics of Peanut ( Arachis hypogaea L.) In Guilan Province, Iran Mohammad et. al., 2009

29. Calcium levels (kg/ha ) Calcium levels (kg/ha) The effect of different levels of Ca on peanut pod yield & kernel yield World Applied Sciences Journal 16 (4): 540-546, 2012

30. Conclusions : The yield of pod and kernel also increased with increasing of calcium application along with potassium. The highest yield of pod (5650 kg/ha) and kernel ( 4622kg/ha) were obtained from 90kg calcium from gypsum. The highest oil content (46.22%) was obtained in 90 kg calcium and 30 kg potassium (interaction effect ). applying of these fertilizers had no significant effect on protein content of peanut kernel . According to the results it could be said that the efficient application of fertilizers, especially potassium along with essential elements such as calcium and sulfur is an important factor for increasing of growth and yield of peanut. Therefore , consideration of suitable proportion of calcium and potassium can have acceptable yield of peanut.

31. Effect of calcium fertilization on shelling percentage, seed and pod yield (kg ha-1) of groundnut (Kg/ha) groundnut International Research Journal of Agricultural Science and Soil Science Vol - 1(8 ): 326-331,2011 Kamara et al., 2009

32. Conclusions : Calcium application significantly (p ≤ 0.001) influenced seed and pod yield The treatments with 100 kg Ca / ha gave the highest seed yield (2065 kg ha-1) and were significantly (p≤ 0.05) different from the control but not significantly different from the 200 kg Ca ha-1 Calcium application increased seed yield by 49 % Calcium application also significantly (p ≤ 0.001) influenced shelling percent, seed and pod yields

33. PARAMETERS SEEDLING EMERGENCE 9DAS 11DAS 13DAS V 1 V 2 V 3 V 1 V 2 V 3 V 1 V 2 V 3 CONTROL(T 1 ) 85.18 80.55 86.11 92.59 86.72 84.25 87.83 87.03 86.10 DISTILLED WATER(T 2 ) 88.88 82.40 88.88 90.12 88.51 89.19 87.77 87.96 90.74 Mg(NO 3 ) (T 3 ) 91.66 95.00 92.58 93.51 93.51 93.51 95.37 94.44 95.37 SEM+ 2.58 2.58 4.47 1.91 1.91 3.00 2.13 2.13 3.69 C.D AT 0.05 5.45 5.45 9.44 4.04 4.04 7.00 4.49 4.49 7.78 V 1 =KHI-536; V 2 =CM-211; V 3 =CM-119 Effect of pre sowing treatment with distilled water and magnesium nitrate to the seeds on germination percentage and height per plant up to collar (cm) of maize varieties Krishnotar ., et al(2009 ) physiological plantarum, vol - 41(1);71-77

34. Mean Yearly Depletion Of Crop Soil-mg In Different Periods (Old Lands). El- Fouly et al. African Journal of Agricultural Research Vol. 5(10), pp. 1060-1067, 2010

35. Sulphur fertilizer effects on grain yield and the sum of physiological indices of canola ( Brassica napus L.) Annals of Biological Research, 2012, 3 (11 ): 5034-5041 Sharifi , 2007

36. Conclusions : Maximum number of grain per pod was recorded at application of 75 kg S ha-1 (22.5) and minimum of it was recorded at 0 kg S ha-1 (14.3 ). Means comparison indicated that maximum grain per pod (23.57) was observed for opera cultivar in application of 75 kg S/ha, while minimum (8.87) of it was recorded for Fornax cultivar in application of zero kg S/ha. The results obtained suggesting that increase in the rate of S resulted in a higher seed yield.

37. Response of groundnut ( Arachis hypogea) to Boron and lime application in acid Alfisols of Jharkhand Asha kumari sinha et. al., 2007

38. Journal of farming systems research and development 14 (1), 2008, 89-94 Interaction effect of boron and lime on quality parameters of groundnut

39. Conclusions : The results indicated that application of B@ 1 kg/ha increased the pod yield of groundnut significantly, which was at par with 1.5 kg B/ha The yield increase was to the tune of 33.7 & 36.65% for 1.0 &1.5 kg B/ha over no B application Application of lime in furrow further increased the response to an extent of 50.6 % over control Positive response was observed in case of oil content which increased from 32.2% in control to 47.1 % in case of 1.5 kg/ha + lime

40. Effect of boron on yield and boron and nitrogen concentration of plant tissue of different varieties of wheat ( Triticum aestivum ) under boron deficient soil Journal of Crop and Weed 4(1) : 46-48 (2008) Mandal et. al., 2005

41. Conclusions : Addition of boron increased grain yield of different varieties of wheat and the range varied from 7.6 % (Sonalika) to 266.2 % (HD 1982). Among the six varieties, Sonalika did not response to Boron. Increase in grain yield of different varieties of wheat with 12 kg ha-1 of borax except for sonalika

42. Paddy : straw ratio Response of rice to Zinc-application and different N-sources in calcareous soil Rahman et. al T1 - 100 kg N/ha as urea, with no zinc. T2 - 100 kg N/ha as urea, with 10 kg ZnSO4/ha. T3 - 100 kg N/ha as ammonium sulfate, with no zinc . T4 - 100 kg N/ha as ammonium sulfate, with 10 kg ZnSO4/ha . T5 - 100 kg N/ha as calcium ammonium nitrate (CAN ), with no zinc. T6 - 100 kg N/ha as calcium ammonium nitrate (CAN ), with 10 kg ZnSO4/ha T7 - 100 kg N/ha as ammonium nitrate (AN), with no zinc. Quarterly SCIENCE VISION Vol.8(1) :100-104, 2002

43. Conclusions : Different nitrogen sources, used along with zinc, significantly increased paddy and straw-yield of rice Rice gave significantly higher yield as 25% in grain and 14 % in straw with ammonium sulfate – zinc The higher paddy to straw ratio in ammonium sulfate-Zn was possibly due to availability of more Zn and more number of filled grains under reduced pH