3/21/2016 UNDERSTANDING PHOSPHORUS IN PLANTS AND SOILS Agronomy Department Iowa State University • • • • • • TOPIC OUTLINE Importance and Abundance Deficiency symptoms Phosphorus cycle in soils Organic soil P Inorganic soil P Factors affecting P availability Importance of P • Essential element for all life forms • Source of energy – e.g. N2 fixation 16ATP + N2 rhizobia 16ADP + 16Pi + energy + 2NH3 •Adequate P enhances physiological processes: – Photosynthesis – Increased root growth – Flowering – Fruiting – Grain production – Earlier crop maturity – Greater stalk strength – Improve overall quality 1 3/21/2016 Abundance of P • In lithosphere is about 0.12% • Present in soils, rocks, water, and plant and animal remains (No gaseous form) • Inorganic or organic forms • Total P is 1000-2000 lbs/ac in furrow slice •Available soil P concentration usually less than 0.1 mg/L in soil solution (0.2 to 0.4 mg/L needed to maximize plant growth) Deficiency Symptoms • Stunting of the plant during early growth • Shriveled grain • Abnormal discoloration such as in corn. The plants are usually dark bluish-green in color with leaves and stem becoming purplish • Reduced growth and yield • Delayed maturity 2 3/21/2016 Corn Deficiency Symptoms Deficiency Symptoms The Phosphorus cycle The concentration of P in solution is determined by three factors 1. adsorption/desorption reactions 2. mineralization/immobilization 3. precipitation/dissolution reactions 3 3/21/2016 The Phosphorus cycle The Phosphorus Cycle • Uptake: by plant roots • Adsorption: removal of ionic P (H2PO4-, HPO42-) from solution by reaction with solid phase of soil. • Desorption: occurs when the orthophosphates, H2PO4- and HPO42- release into the soil solution • Dissolution: dissolve and increase the concentration of soil solution P • Precipitation: as secondary minerals Ca, Fe, Al – P • Immobilization: available P is taken up by soil microbes • Mineralization: conversion of organic P to inorganic P Soil Organic P • 15-80% of total P – Not directly available, must first be mineralized • Inositol hexaphosphate (phytic acid) 2-50% • Nucleic acids, phospholipids, sugar phosphates 1-5% • Carbon to P ratio in organic matter is 100 to 200 – Determines net mineralization or immobilization • Nature of more than 50% of organic P is unknown 4 3/21/2016 Abundant Organic P Forms in Soils R―O―P―OH OH Monoester-P O O R―O―P―OH OR1 Diester-P Inositol Hexaphosphate or Phytic acid Dynamics of P in Soil Nonlabile Soil P slow Labile Soil P fast Solution P < 0.01 mg P L-1 in infertile soils 1 mg P L-1 in well-fertilized soils 7-8 mg P L-1 in recently-amended soils Inorganic P in Soils • High pH – P complexes with Ca and Mg • pH below 7.5 – P complexes with hydrous oxides of Al, Fe, and Mn • Insoluble Al, Fe, and Mn – P form below pH 5.5 5 3/21/2016 Inorganic P in Soils • Apatites (compounds of very low solubility that tend to be present more in nonacid soils than in acid soils): • Hydroxyapatite Ca10(PO4)6OH2 • Fluorapatite Ca10(PO4)6F2 • Calcium phosphates (Forms of P that tend to form when P fertilizers are added to nonacid soils.): • • • • Monocalcium phosphate Ca(H2PO4)2 . H2O Dicalcium Phosphate Ca(HPO4) . H2O Tricalcium Phosphate Ca3(PO4)2 Octacalcium phosphate Ca8H2(PO4)6 5. H2O Inorganic P in Soils • Aluminum phosphates (Forms of P that tend to form when P fertilizers are added to acid soils that have Al.) • Variscite AlPO4. 2H2O • Taranakite H6K3Al5(PO4)8 .18H2O • Wavellite Al8(OH3(PO4))2 • Iron phosphates (forms of P that tend to form when P fertilizers are added to acid soils that have Fe.) • Vivanite Fe3(PO4)2 .8H2O (reduced Fe) • Strengite FePO4.H2O (oxidized Fe) Factors Affecting P Availability • Soil pH – Highest near pH 6.5 – Most important reason for liming in acid soils 6 3/21/2016 Factors Affecting P Availability • Type of Clay – Oxide clays: contain a lot of Al3+ and Fe3+ that can absorb P ions. Low availability because P held very strongly – Kaolinite (1:1) clays, have lots of OH- ions that can be replaced with P ions ---- low availability – Montmorillonite, Illite, etc (2:1) clays: have few OH- ions and they are mostly inaccessible, low anion exchange capacity and adsorb little P Factors Affecting P Availability • At pH of 7.21, H2PO4- = HPO42- (predominant P absorbed by plants) Mole Fraction of Total P [Total P] = [H3PO4°] + [H2PO4-] + [HPO4-2] + [PO4-3] 1.0 0.8 0.6 H3PO40 0.4 HPO4-2 H2PO4-1 PO4-3 0.2 0.0 0 2 4 6 pH 8 10 12 14 Factors Affecting P Availability • Temperature – The lower the temperature the slower the P used by plants – Iowa soils are somewhat cold in the spring, so higher P levels are needed than warmer areas • Organic matter decomposition – Release organic P – Organic acids formed can dissolve Ca-P – Complexes Fe and Al 7 3/21/2016 Factors Affecting P Availability • Soil moisture – The amount of P present is proportional to the amount of water present in the soil – Too much water restricts root growth, reduces the amount of P that roots can reach – Low P is more damaging in dry and poorly drained soils than in good air-water relations • Time of reaction – Fertilizer P is slowly converted into less soluble form – Low solubility of P causes slow reaction • • • • • TOPIC OUTLINE (NEXT CLASS) Phosphorus fertilization Fertilizer nomenclature P fertilizer Placement of P fertilizer Environmental implications Phosphorus Fertilization • Soil Test – Based on chemical principles that relate to inorganic P minerals – When the solution P decreases with plant uptake, P minerals can dissolve and be released to resupply soil solution P – The process simulated by chemical extractant 8 3/21/2016 Soil P determination • Mild Acid extractant (Bray P-1) – Used in most eastern and midwestern States (acid soils) – 0.025M HCl + 0.03M NH4F – Not recommended for soils with pH > 7.4 • Stronger acids (Bray P-2) – 0.1MHCl + 0.03M NH4F – Is not suitable for Iowa soils, too acid especially in high lime soils (Harps) – Give high readings on these soils • Mehlich III – Used in various regions – 0.0015M NH4F + 0.2M CH3COOH + 0.25M NH4NO3 + 0.013M HNO3+EDTA – The same manner as Bray P-1 Extracting Solution • Distilled water – Does not extract much – low extraction • Alkaline extractant (Olsen test) – 0.5M NaHCO3 at pH 8.5 – Used in neutral to calcareous soils – Used in most western states where most soils are alkaline Soil test Classifications % of maximum yield Soil tests classifications indicate whether or not adding a nutrient is likely to result in a yield increase. 100 50 Soil test: Very low low medium/optimum high Fertilizer response likely. very high Response to fertilizer not likely. 9 3/21/2016 Recommendations Recommendations for P are based on soil tests: Determine how much needs to be added to reach optimum soil test levels: the fertilizer uptake efficiency. P Recommendations for Various Crops Soil Test Category Corn (grain) Soybean Wheat Corn/Sorghum Alfalfa (silage) Very Low 100 80 --------------P2O5 to apply (lb acre-1) --------------60 120 110 Low 75 60 50 100 80 High 0 0 0 0 0 Optimum 58 40 30 80 65 Adapted from ISU Extension PM 1688 Rev Oct 2013 10 3/21/2016 Phosphorus Fertilization • P Fertility Evaluation – Plant test • Deficiency symptoms (stunting, purple color, deformation of grain – shriveled grain) – Sap test • Can be used to verify deficiency suspicions: adequate vs. inadequate – Tissue analysis • Optimum for P approximately 0.3% for corn and many other crops Phosphorus Content of Fertilizer • Usually expressed as %P2O5 (old chemist nomenclature from Liebig) • P2O5 = phosphorus oxide Amount of P in fertilizers Rate of P to apply in recommendations Lb P2O5/acre • H2PO4 , HPO42 = ionic forms of P that plants use - - Mined Phosphorus • 90% of the world’s estimated P reserves are found in five countries: Morocco, China, South Africa, Jordan and the United States • Reserves remaining 40 years or 400 years? • Peak P Nature 2009 11 3/21/2016 Cordell et al. 2009_ The story of phosphorus: Global food security and food for thought TED Talk – “A simple solution to the coming phosphorus crisis” by Mohamed Hijri Manufacturing process for common solid and liquid P fertilizers from rock phosphate Symbol Compound P Fertilizers Formula % 11-52-0 TSP Triple superphosphate Ca(H2PO4)2 MAP Monoammonium phosphate NH4H2PO4 TPP1 Triammonium pyrophosphate (NH4)3HP2O7 DAP 1Main Diammonium phosphate in liquid form (NH4)2HPO4 0-46-0 10-34-0 18-46-0 12 3/21/2016 Phosphorus Content of Fertilizer • % P = 0.44 x % P2O5 (2 x Atomic. wt. P)/(Mol. wt. P2O5)= (2 x 31)/([2 x 31]+ [5 x16]) = 0.4366 • % P2O5 = % P x 2.29 (Mol. wt. P2O5)/(2 x Atomic wt. P) = ([2 x 31]+ [5 x 16])/(2 x31)=2.29 Fertilizers are designed to have a known "grade" or concentration of nutrients. For example, the fertilizer shown below has a 20-5-10 grade, meaning it is 20% N, 5% P205, and 10% K2O by weight. The concentration of nutrients in the fertilizer is multiplied by the amount of the fertilizer material applied per acre to find the actual amount of N, P205, and K2O applied per acre. For example, if 100 lbs of the fertilizer above were applied evenly over an acre, you would apply: 20% N x 100 lbs fertilizer/acre = 20 lbs N/acre 5% P205 100 lbs fertilizer/acre = 5 lbs P205/acre 10% K2O x 100 lbs fertilizer/acre = 10 lbs K2O/acre On the other hand, if you wanted to satisfy a crop P fertilizer guideline of 15 lbs P205/acre with that same fertilizer, you would.... (15 lbs P205/acre) / (0.05) = 300 lbs/acre of the fertilizer would need to be applied In this case, the crop P205 guideline is divided by the concentration of P205 in the fertilizer and the amount of fertilizer material to be applied per acre is calculated! 13 3/21/2016 Phosphorus Content of Fertilizer Triple superphosphate (0-46-0) costs $280 per ton. What is the cost per pound of P2O5? First, calculate the pounds of P2O5 in the fertilizer: 2,000 lbs fertilizer x 0.46 = 920 lbs. Next, calculate the cost per pound of P2O5: $280 / 920 lbs = $.30/lb P2O5. Classification of P Fertilizer Based on Solubility • Water soluble – Usually small amount, available quickly and may react quickly to unavailable forms • Citrate soluble – Dissolve in 1N ammonium citrate – “available” (printed on the bag) – Why citrate? Citrate is mild acid and high buffer capacity to approximate plant P availability Total P = all that is present, regardless of availability Competing Uses for Phosphorus • • • • • • Detergents Pesticides Explosives (matches to bombs) Nerve agents Water softeners Metals manufacturing (steel and bronze) 14 3/21/2016 • Manure P Fertilizers – Beef manure = 10 + 5 + 10/ton wet – Hog manure, the same or little higher in P – Chicken and sheep manure, 2x as much P as cattle Manure management plans will continue to play a major role in managing P fertility for plant growth as rock phosphate reserves are depleted and transportation costs continue to rise http://www.iowadnr.gov/afo/mmp.html Iowa DNR Animal Feeding Operations http://www.midwestagnet.com/Global/story.as p?S=12062705 Late Winter Manure Application and Risk Angela Rieck-Hinz is an extension program specialist for Iowa State University Extension and is the coordinator of the Iowa Manure Management Action Group (IMMAG). Rieck-Hinz can be reached at (515) 294-9590 or by emailing amrieck@iastate.edu. Placement of P Fertilizer • To Broadcast or Band apply: That is the question? • P is not mobile and not soluble (placement can be important): – Most important if soil test P is low – close to the seed – As soil test P increases, placement close to the seed is less important • P fixing soils - highly weathered soils – Placement in a band, reduces surface soil/fertilizer contact, reduces the rate of fixation • Banded Starter placement – 2” below and 2” to the side of the seed – Purpose: offset cool soils 15 3/21/2016 Why Broadcast? Can apply large amounts conveniently Ideal for building soil fertility Minimizes risk of fertilizer injury On fields of low fertility, banded starter P may not be adequate for maximum yield • Combinations of broadcast and band applications produce the highest yields on low testing soils • • • • Placement of P Fertilizer Band Application • Overwhelms soil fixation capacity • Places nutrients near the seedling – Roots intercept early and proliferate near the band – Including ammonium-N, slows P fixation and lowers pH near the root to improve both P and micronutrient availability • Favors the crop over the weeds • Keeps nutrients away from the surface – Reduces runoff P concentrations 16 3/21/2016 Phosphorus and Environmental Concerns • P losses from cropland can cause surface water quality problems • Soil P levels have increased • Manure P is a major contributor to soil P buildup • Land application of manure is often the only practical management option The Fate of Phosphorus Transport Phosphorus and Water Quality • Phosphorus losses from agriculture can be a major source of P entering lakes and streams. • Phosphorus additions to natural waters can stimulate weed and algae growth. • Vegetative growth -> oxygen depletion (aka hypoxia) -> reduced water quality. 17 3/21/2016 Eutrophication Caused by Excessive P 18