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  2. 2. PROLOGUE ABOUT INORGANIC/ ORGANIC/CHELATED/ PROTEINATED/ NANO MINERALS Conventional animal nutrient supplements including A) Minerals B) Amino acids C) Vitamins D) Drugs have certain specific inherent drawbacks like 1) Poor bio-absorbability 2) Toxicity 3) Unpalatable taste 4) Poor solubility 5) High bio-absorption inhibiting activity (High reactivity) Science long back recognized that the body must have certain minerals to accomplish its work and preserve its health. However, recently Modern Science conceives that these minerals must be in their Chelated, Proteianated, Organic, Colliodal or Nano state to do the consumer any use at all; based on the following observations. 1. Minerals are inorganic as they exist naturally in the soil and water. 2. Minerals are organic as they exist in plants and animals. 3. Only plants can transform inorganic minerals into organic minerals. 4. Animals must eat plants or plant-eating animals to obtain their organic minerals. 5. Inorganic minerals are useless and injurious to the animal organism. Minerals and mineral mixes and premixes used in animal feed can contain contaminants such as dioxin and various heavy metals. Some mineral mixes and premixes are by-products or co-products of industrial metal production and can become contaminated. For example, mineral mixes containing zinc oxide obtained from brass production have been found to have high levels of dioxin contamination. FDA has issued an alert to the feed industry warning against the use of mineral mixes and premixes that are by-products or co-products of industrial metal production (FDA CVM Update, 2003). EPA is aware that hazardous wastes are sometimes recycled as nutritional supplements in animal feed preparations but does not necessarily consider this use
  3. 3. to constitute disposal of hazardous waste. For example, zinc oxide reclaimed from emission control dust from electric arc furnaces is a listed hazardous waste, but EPA permitted it to be used as a nutritional feed supplement for animals (EPA, 1994). Minerals may also contain heavy metal contaminants such as lead, arsenic, cadmium, and mercury. AAFCO lists 133 different mineral products used as feed ingredients, and the “typical” levels of these contaminants in mineral feed ingredients. Lead is considered only “moderately toxic” by the American Association of Food Control Officials (AAFCO), and the maximum tolerance in complete feed is 30 ppm. Because inorganic minerals and organic minerals have the same chemical compositions, they were being treated as same, for a long time by the early nutritionists. The mineral, iron, in the bloodstream has the same chemical composition as the mineral, iron, in a nail—iron is iron, after all. However, only of late, nutritionists visualized the differences between these two forms of iron. Although there was a nutritive similarity between Chelated, Proteinated, Nano, Colloidal, Organic and Inorganic minerals, each of these will have different impacts on the performance of the Animals. It is necessary that the minerals in the soil be elaborated into organic compounds by the plant before they can be assimilated by the animal or human body. The various mineral compounds produced synthetically differ in their structure and in the relative positions of their component molecules than those produced in the plant. Over sixty years ago a German scientist named Abderhalden conducted a series of experiments comparing how several species absorbed different forms of iron. He found that animals fed with food poor in iron, plus in addition of inorganic iron, were unable in the long run to produce as much hemoglobin as those, receiving a natural iron-sufficient diet. While the inorganic iron may be absorbed into the body, it is not utilized in the formation of hemoglobin, but remains unused within the tissues. Abderhalden also concluded that any apparent benefit of the inorganic iron resulted from its stimulating effect. Chemically, it is true that iron in the bloodstream and iron in nails are the same and that calcium in rocks (known as dolomite) is identical to calcium in the bones. However, it is a grave error to believe that the body can digest and assimilate and utilize powdered nails and crushed rocks. The word chelate is derived from the Greek word meaning "claw". Technically chelates hold trace elements in suspension while in transit.
  4. 4. A mineral amino acid chelate is composed of an amino acid that has two or more donor groups combined with the mineral so that one or more rings are formed, with the mineral being the closing component of this heterocyclic ring. Chelate structures contain covalent bonds which give these chelates properties that are much different than ionically bonded mineral salt forms. Mineral amino acid chelates are bidentate (the mineral is attached at two ends of amino acid ligand), and have a ring in their structure, while mineral complexes are unidentate (mineral is attached at one end of its ligand) with no ring structure. It has been shown that a bidentate (chelated) glycino group absorbs at the IR wavelength of 1643 cm-1, an ionized unidentate at 1610 cm-1, and a unionized unidentate at 1710 cm-1. In addition, it has been shown that the carboxyl group in the amino acid glycine absorbs at the band of infra-red light of 504 cm-1. The degree of absorption at this band segment has been shown to diminish as the amount of bound glycine increases in a sample. The term “organic mineral” refers to a variety of compounds including metal-amino acid complexes, metal amino chelates, metal proteinates, metal-polysaccharide complexes, metalyeast complexes, and metal-organic acid complexes. (Patton, 1990) An organic mineral is simply a combination of a metal ion with an organic ligand such as amino acids, proteins, polysaccharides, yeast, or organic acids. Specifically, the metal ion is bound to the organic ligand through multiple attachments (either ionic or covalent) with the metal ion occupying a central position in the structure (Kincaid, 1989, Nelson, 1988). During organic mineral formation, the metal ion and organic ligand act as mutual electron donors (ligand) and electron acceptors (metal cations) forming a heterocyclic ring structure (Nelson, 1988). Generally, the metal ion is attached to electronegative areas (two or more) on a ligand. The minerals can be absorbed along with the amino acids as a single unit utilizing the amino acid(s) as a carrier molecule. Therefore, the problems associated with the competition of ions for active sites and the suppression of specific nutritive mineral elements by others can be avoided. Interest is also building in using organic trace minerals in place of a portion of the feed inorganic mineral supplement in order to get maximum growth and health with lower levels of mineral intake, thus lowering the amount of minerals excreted from the birds (Bao et al., 2006). Reducing mineral levels in litter placed on the land is an issue in many countries and lower levels of complexed trace minerals may aid in reducing litter mineral excess. A number of minerals have been shown to play crucial roles in broiler health and organic trace minerals have been shown to have a role in boosting cellular and humoral immunity in broilers. Organic zinc compounds have shown benefits in improving immunity in birds (Pimental et al., 1991a; Kidd et al., 1994).
  5. 5. In addition, chicks hatched from breeder hens fed organic trace minerals have shown improved cellular and humoral immunity as well (Kidd et al., 1992; Kidd et al., 1993). The neutralization of stomach acid by pancreatic secretions into the intestine could have negative consequences on mineral absorption because without the influence of acid, some minerals may not remain dissociated and may bind with other components present in the intestinal contents, rendering them unavailable for absorption. One way this problem can be avoided is for the mineral to be surrounded by “ligands,” or weak binding agents, which will protect the mineral from stronger binding agents, even in the absence of acid, yet allow normal absorption to occur. SALIENT FEATURES OF PROTEINATED MINERALS 1. Counteracts Anti Nutritional Factors, which affect the mineral absorption 2. Health improvement (immune status, functional nutrition) 3. Improve the bioavailability of minerals 4. Improvement in the quality of animal produce (meat, milk, egg, wool etc.,) 5. Ensures over all animal welfare 6. Performance improvement 7. Protects environment by reducing metal pollution through excreta. 8. Reduces degenerative effect of trace minerals on vitamins in premixes and feed. 9. Reduction of antagonism, interferences and competition among minerals.
  7. 7. Strategies used to synthesize nanoparticles Traditionally nanoparticles were produced only by physical and chemical methods. Some of the commonly used physical and chemical methods are ion sputtering, solvothermal synthesis, reduction and sol gel technique. Basically there are two approaches for nanoparticle synthesis namely the Bottom up approach and the Top down approach. In the Top down approach, scientists try to formulate nanoparticles using larger ones to direct their assembly. The Bottom up approach is a process that builds towards larger and more complex systems by starting at the molecular level and maintaining precise control of molecular structure. Physical and chemical methods of nanoparticle synthesis Some of the commonly used physical and chemical methods include: Sol-gel technique, which is a wet chemical technique used for the fabrication of metal oxides from a chemical solution which acts as a precursor for integrated network (gel) of discrete particles or polymers. The precursor sol can be either be deposited on the substrate to form a film, cast into a suitable container with desired shape or used to synthesize powders. Solvothermal synthesis, which is a versatile low temperature route in which polar solvents under pressure and at temperatures above their boiling points are used. Under solvothermal conditions, the solubility of reactants increases significantly, enabling reaction to take place at lower temperature. Chemical reduction, which is the reduction of an ionic salt in an appropriate medium in the presence of surfactant using reducing agents. Some of the commonly used reducing agents are sodium borohydride, hydrazine hydrate and sodium citrate. Laser ablation, which is the process of removing material from a solid surface by irradiating with a laser beam. At low laser flux, the material is heated by absorbed laser energy and evaporates or sublimates. At higher flux, the material is converted to plasma. The depth over which laser energy is absorbed and the amount of material removed by single laser pulse depends on the material’s optical properties and the laser wavelength. Carbon nanotubes can be produced by this method. Inert gas condensation, where different metals are evaporated in separate crucibles inside an ultra high vacuum chamber filled with helium or argon gas at typical pressure of few 100 pascals. As a result of inter atomic collisions with gas atoms in chamber, the evaporated metal atoms lose their kinetic energy and condense in the form of small crystals which accumulate on liquid nitrogen filled cold finger. E.g. gold nanoparticles have been synthesized from gold wires.
  8. 8. NANO PARTICLES OF MINERALS Current research is going on regarding the use of magnetic nanoparticles in the detoxification of military personnel in case of biochemical warfare. It is hypothesized that by utilizing the magnetic field gradient, toxins can be removed from the body. Enhanced catalytic properties of surfaces of nano ceramics or those of noble metals like platinum and gold are used in the destruction of toxins and other hazardous chemicals (Salata, 2005). Photocatalytic activity of nanoparticles has been utilized to develop self- cleaning tiles, windows and anti- fogging car mirrors. The high reactivity of Titanium nanoparticles either on their own or when illuminated by UV light have been used for bactericidal purposes in filters. An important opportunity for nanoparticles in the area of computers and electronics is their use in a special polishing process, chemical-mechanical polishing or chemical-mechanical planarization (CMP), which is critical to semiconductor chip fabrication. CMP is used to obtain smooth, flat, and defect-free metal and dielectric layers on silicon wafers. This process utilizes slurry of oxide nanoparticles and relies on mechanical abrasion as well as a chemical reaction between the slurry and the film being polished. CMP is also used in some other applications, such as the polishing of magnetic hard disks. Nanoscale titanium dioxide and zinc oxide have been used as sunscreens in cosmetics. The primary advantage of using these nanoparticles is that they are well dispersed and transmit visible light, acting as transparent sunblocks. On the other hand, inorganic sunscreens appear white on the skin- a potential drawback. The interaction of silver nanoparticles with HIV I has been demonstrated in vitro. It was shown that the exposed sulfur binding residues of the glycoprotein knobs were attractive sites for nanoparticle interaction and that the silver nanoparticles had preferential binding
  9. 9. to the gp 120 glycoprotein knobs. Due to this interaction, it was found that the silver nanoparticles inhibited the binding of the virus to the host cells in vitro (Elechiguerra et al., 2005). Magnetic nanoparticles are also used in targeted therapy where a cytotoxic drug is attached to a biocompatible magnetic nanoparticle. When these particles circulate in the bloodstream, external magnetic fields are used to concentrate the complex at a specific target site within the body. Once the complex is concentrated in the target, the drug can be released by enzymatic activity or by changes in pH or temperature and are taken up by the tumour cells (Pankhurst et al., 2003). Porous nanoparticles have also been used in cancer therapy where the hydrophobic version of a dye molecule is trapped inside the Ormosil nanoparticle. The dye is used to generate atomic oxygen which is taken up more by the cancer cells when compared to the healthy tissue. When the dye is not entrapped, it travels to the eyes and skin making the patient sensitive to light. Entrapment of the dye inside the nanoparticle ensures that the dye does not migrate to other parts and also the oxygen generating ability is not affected. Alivisatos (2001) reported the presence of inorganic crystals in magnetotactic bacteria. The bacterium was found to have about 20 magnetic crystals with a size range of 35- 120nm diameter. The crystals serve as a miniature compass and align the bacteria with the external magnetic field. This enables the bacterium to navigate with respect to the earth’s magnetic field towards their ideal environment. These bacteria immobilize heavy metals from a surrounding solution and can be separated by applying a low intensity magnetic field. This principle can be extended to develop a process for the removal of heavy metals from waste water. Bioremediation of radioactive wastes from nuclear power plants and nuclear weapon production, such as uranium has been achieved using nanoparticles. Cells and S layer proteins of Bacillus sphaericus JG A12 have been found to have special capabilities for the clean up of uranium contaminated waste waters (Duran et al., 2007). Gold nanoparticles are widely used in various fields such as photonics, catalysis, electronics and biomedicine due to their unique properties. E. coli has been used to synthesize gold nanoparticles and it has been found that these nanoparticles are bound to the surface of the bacteria. This composite may be used for realizing the direct electrochemistry of haemoglobin (Du et al., 2007). p- nitrophenol is widely used in pesticides, pharmaceutical industries, explosives and in dyes and is known to be a carcinogenic agent. Gold nanoparticles have been synthesized using the barbated skullcap extract. The nanoparticles synthesized by this method have been modified to the glass electrode and this has been used to enhance the electronic transmission rate between the electrode and p- nitrophenol (Wang et al., 2009). Tripathy et al., (2008) reported the antibacterial applications of the silver nanoparticles synthesized using the aqueous extract of neem leaves. The nanoparticles were coated on cotton disks and their bactericidal effect was studied against E.coli. Duran et al., (2005) reported the significant antibacterial activities of the silver nanoparticles synthesized using Fusarium oxysporum.
  12. 12. INTRODUCTION P is an important nutrient but the concentration of plant available P is generally low (0.7 to 1.2% of total P) in arid soils. Further, nearly 70% of the applied phosphate fertilizers is converted to -1 unavailable forms after application. Total quantity of P in arid soils is >600 kg ha , but its availability is restricted. Thus, application of phosphate fertilizers is a must for good crop. Phosphate fertilizers are mainly synthesized from rock phosphate. Phosphorus is a nonmetallic chemical element in group 15 (nitrogen family, formerly Va) of periodic table; atomic number 15 atomic mass 30.9738; melting point ca 44.1 C (white); boiling point ca 280 C (white); specific gravity 1.82 (white), 2.34 (red), 2.70 (black); valence -3, +3, or +5 ; electronic config. 2-8-5 or 1s 22s 22p 63s 23p 3. The phosphorus molecule is composed of four phosphorus atoms, P4. Phosphorus exists in a number of allotropic forms [white (alpha and beta), red, black and/or violet] in the same physical state. Phosphorus (P) is an essential mineral that is found in all cells within the bodies of every living being. Phosphorus is primarily found as phosphate. The major building blocks of biology are covalent molecules comprising proteins, polysaccharides, and nucleic acids. The nucleic acids deoxyribonucleic acid (DNA) and ribonucleic acid (RNA) are polymers based on phosphate ester monomers. The high-energy phosphate bond of ATP is the major energy currency of living organisms. Cell membranes are composed largely of phospholipids.
  13. 13. Metabolic functions of Phosphorous Phosphorous provides the energy to cells to multiply and grow. The phosphate ion present in the fertilizers get attached with adenosine moity to synthesize adenosine triphosphate (ATP), the energy currency of cells. Another biomolecule synthesised by the photosynthetic tissue contains phosphate ion, called reduced nicotinamide adenine dinucleotide phosphate (NADPH) that drives the fixation of carbon dioxide to form starch. A variety of enzymatic activities are controlled by alternate phosphorylation and dephosphorylation of proteins. The metabolism of all major metabolic substrates depends on the functioning of phosphorus as a cofactor in a variety of enzymes and as the principal reservoir for metabolic energy. The ability of plants to acquire phosphate-P during deficiency conditions also increases due to the synthesis of phosphate transporters. These biomolecules also transport phosphite ions. Phosphite is rapidly absorbed and translocated within the plant. However, the uptake is pH dependent and subject to competition by phosphate ions. Phosphite in presence of a small quantity of phosphate will not be recognised by phosphate transporters. Despite having similar mobility, the phosphite is a non-metabolized form of phosphorous and plants cannot use this as the sole source of phosphorous. Phosphate can be assimilated into organic P compounds within minutes of uptake. Antagonistic nature of the Minerals.
  14. 14. Phosphorous Deficiency Symptoms: IN AGRICULTURE:  Enhanced root growth at the cost of shoot development  Increased root to shoot ratio  Low yields  Purple (anthocyanin pigment) colouration of leaves and petioles  Purple and weak stems IN ANIMALS: Phosphorus deficiency in cattle may cause symptoms related to reduced appetite, including retarded growth rate of young cattle, low milk yield and impaired fertility. Skeletal abnormalities associated with osteomalacia may appear as stiffness, reluctance to move, shifting lameness, cracking sounds in joints when walking, an arched back and in severe cases, spontaneous fractures.
  15. 15. Sources of Phosphorous: Percentages of water-soluble and available phosphate in several common fertilizer sources. P 2 O 5 K P 2 O 5 Source N Total Available Water Soluble* - - - - - - - - - - - - - - - % - - - - - - - - - - - - - - Superphosphate (OSP) 0 21 20 85 0 Concentrated Superphosphate (CSP) 0 45 45 85 0 Monoammonium Phosphate (MAP) 11 49 48 82 0 Diammonium Phosphate (DAP) 18 47 46 90 0 Ammonium Polyphosphate (APP) 10 34 34 100 0 Rock Phosphate 0 34 3-8 0 0 COLION_P 0.95 45 45 100 0 *Water-soluble data are a percent of the total P2O5 Source: Ohio Agronomy Guide. Ohio Cooperative Extension Service Bull.472. Pure anhydrous phosphoric acid is a white solid that melts at 42.35 °C to form a colorless, viscous liquid. Most people and even chemists refer to orthophosphoric acid as phosphoric acid, which is the IUPAC name for this compound. The prefix ortho is used to distinguish the acid from other phosphoric acids, called polyphosphoric acids. Orthophosphoric acid is a non-toxic, inorganic, rather weak triprotic acid, which, when pure, is a solid at room temperature and pressure. The chemical structure of orthophosphoric acid is shown above in the data table. Orthophosphoric acid is a very polar molecule; therefore it is highly soluble in water. The oxidation state of phosphorus (P) in ortho- and other phosphoric acids is +5; the oxidation state of all the oxygen atoms (O) is -2 and all the hydrogen atoms (H) is +1. Triprotic means that an orthophosphoric acid molecule can dissociate up to three times, giving up an H+ each time, which typically combines with a water molecule, H2O, as shown in these reactions: H3PO4(s) + H2O(l) H3O+ (aq) + H2PO4 – (aq) Ka1= 7.25×10−3 H2PO4 – (aq)+ H2O(l) H3O+ (aq) + HPO4 2– (aq) Ka2= 6.31×10−8 HPO4 2– (aq)+ H2O(l) H3O+ (aq) + PO4 3– (aq) Ka3= 3.98×10−13 The anion after the first dissociation, H2PO4 – , is the dihydrogen phosphate anion. The anion after the second dissociation, HPO4 2– , is the hydrogen phosphate anion. The anion after the third dissociation, PO4 3– , is the phosphate or orthophosphate anion. For each of
  16. 16. the dissociation reactions shown above, there is a separate acid dissociation constant, called Ka1, Ka2, and Ka3 given at 25°C. Associated with these three dissociation constants are corresponding pKa1=2.12 , pKa2=7.21 , and pKa3=12.67 values at 25°C. Even though all three hydrogen (H ) atoms are equivalent on an orthophosphoric acid molecule, the successive Ka values differ since it is energetically less favorable to lose another H+ if one (or more) has already been lost and the molecule/ion is more negatively-charged. Phosphite is the fungicidal form of phosphorous that is not recognised by roots for uptake and metabolism compared to the most acceptable form called phosphate. Although, phosphite can get oxidised by soil microbes to phosphates , but most recent research has shown that phosphate reduced the root and shoot growth @ 24 kg/ha (Barrett, 2002). McDonald et al., 2001 found that phosphite is not utilized, but may trick phosphorus deficient plants into not mimicking typical P deficiencies. Wells et al., (2000) found that toxicity symptoms in alfalfa disappeared after 21 days. Harris (2003) applied both phosphate and phosphite starter and foliar fertilizers on cotton to compare its growth response to different P sources, and found that phosphite treated plants were shorter compared to phosphate treated plants Phosphites should not be used as a substitute for plant – available , orthophosphate forms of phosphorous . Phosphite is not immediately plant available and could lead to plant toxicities in sensitive crops if high rates are applied . Phosphite damage appears amazingly similar to glyphosate injury to crops. MECHANISMS INVOLVED IN USING SUPER PHOSPHATE IN SOIL. The following article was written by Soiltech Soil Scientist, Dave McKie MAgSc (Hons) 1. Formation of Metal Phosphates After Super has been applied and while it is being assimilated into the soil, dissolution- precipitation processes are active. These involve both the formation of and subsequent dissolving of phosphate precipitates. The fertiliser granules on the soil surface attract moisture to them, resulting in chemical reactions which convert the soluble P within the granules into phosphoric acid and a less soluble form of P, di-calcium phosphate. If the prevailing soil conditions are acidic, and good levels of iron, aluminium, or manganese are present, the P from the granules can be transformed into low solubility phosphates of these metals. On the other hand, if the overall soil pH is neutral or alkaline, and adequate levels of calcium are present, di-calcium phosphate can be further converted to an insoluble tri-calcium phosphate, a compound similar to naturally occurring rock phosphate. The latter scenario is believed to be more important to the overall
  17. 17. concentration of P in soil solution and thus also to plant P nutrition. Maintaining an overall soil pH 6-6.5 lessens the likelihood of P precipitation and enhances P solubility. During the assimilation process, an acid laden solution of low pH (1.5) moves out into the soil. This is hostile to soil biology and, as a result, any biological life in the vicinity of the disintegrating Super granule is wiped out. The impact of a fertiliser on soil biology is often ignored when fertilizer is applied, yet soil biology is critical to the plant uptake of nutrients from the soil. How long these adverse acid conditions continue varies depending on other soil factors but eventually the pH returns to levels close to that which existed before the fertiliser was applied. The application of ammonium phosphate fertilisers also lowers pH during assimilation but not as severely as Super does. Dicalcium phosphate and RPR fertilisers do not lower pH when being assimilated and are thus “friendly” to the organisms living within the soil. The latter fertilisers also release P more slowly and at a rate which more closely complements plant P requirements. Plants are unable to uptake all of the initial soil solution flush of P from Super. Although Super lowers pH around the granules during the assimilation phase, this situation is not permanent. In terms of overall soil pH, Super only slightly increases overall soil acidity. 2. Absorption on Soil Particles Sorption-desorption processes play a significant role in removing soluble inorganic P from soil solution. Sorption occurs when P is removed from the soil solution and becomes attached or fixed to the surface of soil particles. The impact of sorption varies depending on the nature and extent of the particle and aggregate surfaces within the soil, but it is generally worse in ash derived soils and other soils with a large content of amorphous or poorly structured material. Such soils have a large available surface area to which P can become fixed. Once the initial dissolution-precipitation reactions outlined above have run their course, sorption-desorption processes become the main controller of soil solution P concentration. In time, and again depending on other prevailing soil factors, the P absorbed on these soil surfaces either slowly penetrates deeper into the fabric of the soil material or becomes buried beneath iron and aluminium oxide coatings which form on the surface of soil particles. When this occurs the P is said to be “occluded”. It is sometimes assumed that P fixation processes are always in the direction of loss of P from soil solution. This is not correct. P is also released back into soil solution from soil surfaces by the reverse process, desorption. However, the P that has penetrated within soil particles or become occluded is only released very slowly, and then not until surface absorbed P reserves have been depleted. Release of penetrated P generally occurs too slowly to maintain soil solution P concentrations at a high enough level for good plant growth. 3. Organic Immobilisation Plants remove P from soil solution through their roots. In time, much of this P is returned to the soil in plant litter, roots etc and in animal dung. Because dung is often deposited at
  18. 18. stock camps or in races etc, dung transfer can result in loses of P from the system, or at best uneven re-distribution of P. Obviously, some P is also lost in products/commodities that are removed from the farm. P is constantly being cycled through soil organic matter. It is constantly being incorporated into the plant and then subsequently released and made available again and so on. Soil microbes, soil animals and other soil biological life also remove P from soil solution. The life cycle of the microbes is usually quite short and hence, after they die, the P is released again, generally with a much faster turn around than occurs with plant P. Microbial P is returned to soil solution in both organic and inorganic soluble P forms. Just like the P immobilised in plants, so also the P in soil organisms is recycled either through other soil organisms, or back into plants or else it is subjected to the other processes described earlier. Soil biological life plays a key role in the mineralization of P from both organic and non organic sources. In many pastoral situations, organic material can often comprise 50 – 80% of the total P in the soil. Not all of this P is plant available or even becomes plant available P in the short term. However, the microbial biomass P is usually re-cycled quite rapidly when soil conditions favour these organisms. For instance, in a typical soil with say 1000kg/ha of total P within the plant rooting zone and a microbial biomass comprising say 3% of the total soil P, P re- cycled from this source could supply roughly 15-24kg of P/yr or the equivalent of an annual application of 250kg/ha of Super! In a manner similar to the way soil solution P is subject to sorption-desorption processes on the surface of soil particles, it can also become absorbed onto the surface of organic matter particles within the soil. If conditions are favourable, significant amounts of P can be immobilised in this way, especially as soils become more acid. The chemistry of organic P is complex and not very well understood. Never the less, it is clear that under the influence of soil microbial life, and in particular rhizosphere fungi, a portion of this organic P is returned to soil solution. As a general rule, there is often more organic P in soil solution than inorganic P. When it is considered that the Olsen P test only assesses the inorganic plant available P fraction of the soil, then it becomes clear that the Olsen P test may under-estimate plant available P i.e. there may be much more P available than is commonly realised. Because of the size and complexity of organic soil molecules, it is difficult to assess how much of this soluble organic P is taken up by plant roots but clearly, organic P does contribute to plant P nutrition.
  19. 19. MAGNITUDE OF PHOSPHATIC FERTILIZER PRODUCTION AND USE Worldwide phosphate production for 2010 is expected to be roughly 176 million tonnes per year. China, Morocco and the United States represent roughly 67% of the global phosphate rock supply. Also, roughly 65% of worldwide reserves are located in Morocco with China a distant second. Evolution of fertilizer consumption between 2007/08 and 2010/11 (Adapted from Heffer and Prud’homme, 2012)
  20. 20. ENVIRONMENTAL POLLUTION BY PHOSPHATIC FERTILIZER INDUSTRY Phosphate Fertilizer Mining Waste. Effects of Fluoride Pollution It is well known that where ever phosphate industries have had inefficient, or non- existent, pollution control that has caused a very serious threat of Fluoride. The Canadian Broadcasting Corporation (CBC) called the phophate industry a “pandora’s box.” While the industry brought wealth to rural communities, it also brought ecological devastation. The CBC described the effects of one particular phosphate plant in Dunville, Ontario: “Farmers noticed it first… Something mysterious burned the peppers, burned the fruit, dwarfed and shriveled the grains, damaged everything that grew. Something in the air destroyed the crops. Anyone could see it… They noticed it first in 1961. Again in ’62. Worse each year. Plants that didn’t burn, were dwarfed. Grain yields cut in half…Finally, a greater disaster revealed the source of the trouble. A plume from a silver stack, once the symbol of Dunville’s progress, spreading for miles around poison – fluorine. It was identified by veterinarians. There was no doubt. What happened to the cattle was unmistakable, and it broke the farmer’s hearts. Fluorosis – swollen joints, falling teeth, pain until cattle lie down and die. Hundreds of them. The cause – fluorine poisoning from the air.” Fluoride has been, and remains to this day, one of the largest environmental liabilities of the phosphate industry. The source of the problem lies in the fact that raw phosphate ore contains high concentrations of fluoride, usually between 20,000 to 40,000 parts per million (equivalent to 2 to 4% of the ore).
  21. 21. When this ore is processed into water-soluble phosphate (via the addition of sulfuric acid), the fluoride content of the ore is vaporized into the air, forming highly toxic gaseous compounds (hydrogen fluoride and silicon tetrafluoride). In Polk County, Florida, the creation of multiple phosphate plants in the 1940s caused damage to nearly 25,000 acres of citrus groves and “mass fluoride poisoning” of cattle. It is estimated that, as a result of fluoride contamination, “the cattle population of Polk County dropped 30,000 head” between 1953 and 1960, and “an estimated 150,000 acres of cattle land were abandoned” (Linton 1970). According to the former president of the Polk County Cattlemen’s Association: “Around 1953 we noticed a change in our cattle… We watched our cattle become gaunt and starved, their legs became deformed; they lost their teeth. Reproduction fell off and when a cow did have a calf, it was also affected by this malady or was a stillborn.” In the 1960s, air pollution emitted by another phosphate plant in Garrison, Montana was severe enough to be branded “the worst in the nation” by a 1967 National Air Pollution Conference in Washington, D.C. As in Polk County, and other communities downwind of fluoride emissions, the cattle in Garrison were poisoned by fluoride. As described in a 1969 article from Good Housekeeping: “The blight had afflicted cattle too. Some lay in the pasture, barely able to move. Others limped and staggered on swollen legs, or painfully sank down and tried to graze on their knees… Ingested day after day, the excessive fluoride had caused tooth and bone disease in the cattle, so that they could not tolerate the anguish of standing or walking. Even eating or drinking was an agony. Their ultimate fate was dehydration, starvation – and death.” Litigation from Fluoride Damage Damage to vegetation and livestock, caused by fluoride emissions from large industry, has resulted, as one might expect, in a great deal of expensive litigation. In 1983, Dr. Leonard Weinstein of Cornell University, stated that “certainly, there has been more litigation on alleged damage to agriculture by fluoride than all other pollutants combined” (Weinstein 1983). While Weinstein was referring to fluoride pollution in general, his comments give an indication of the problem facing the phosphate industry – one of the most notorious emitters of fluoride – in its early days. So too does an estimate from Dr. Edward Groth, currently a Senior Scientist at Consumers Union. According to an article written by Groth, fluoride pollution between the years 1957 to 1968, “was responsible for more damage claims against industry than all twenty (nationally monitored air pollutants) combined.” The primary reason for the litigation against fluoride emitters was “the painful, economically disastrous, debilitating disease” that fluoride causes to livestock
  22. 22. (Hodge & Smith 1977). As noted in a 1970 review by the US Department of Agriculture (USDA), “Airborne fluorides have caused more worldwide damage to domestic animals than any other air pollutant” (Lillie 1970). Another review on air pollution reached the same conclusion. According to Ender (1969): “The most important problem concerning damage to animals by air pollution is, no doubt, the poisoning of domestic animals caused by fluorine in smoke, gas, or dust from various industries; industrial fluorosis in livestock is today a disorder well known by veterinarians in all industrialized countries.” According to a review discussing “Fluorine toxicosis and industry”, Shupe noted that: “Air pollution damage to agricultural production in the United States in 1967 was estimated at $500,000,000. Fluoride damage to livestock and vegetation was a substantial part of this amount” (Shupe 1970). Scrubbing away the problem Due to the inevitable liabilities that fluoride pollution presented, and to an increasingly stringent set of environmental regulations, the phosphate industry began cleaning up its act. As noted by Ervin Bellack, a chemist for the US Public Health Service: “In the manufacture of super-phosphate fertilizer, phosphate rock is acidulated with sulfuric acid, and the fluoride content of the rock evolves as volatile silicofluorides. In the past, much of this volatile material was vented to the atmosphere, contributing heavily to pollution of the air and land surrounding the manufacturing site. As awareness of the pollution problem increased, scrubbers were added to strip particulate and gaseous components from the waste gas…” (Bellack 1970) A 1979 review, published in the journal Phosphorous & Potassium, added: “The fluorine compounds liberated during the acidulation of phosphate rock are now rightly regarded as a menace and the industry is now obliged to suppress emissions- containing vapors to within very low limits in most parts of the world… In the past, little attention was paid to the emission of gaseous fluorine compounds in the fertilizer industry. But today fluorine recovery is increasingly necessary because of stringent environmental restrictions which demand drastic reductions in the quantities of volatile and toxic fluorine compounds emitted into the waste gases. These compounds now have to be recovered and converted into harmless by- products for disposal or, more desirably, into marketable products” (Denzinger 1979). A Missed Opportunity: Little Demand for Silicofluorides Considering the great demand among big industry for fluoride chemicals as a material used in a wide variety of commercial products and industrial processes, the phosphate industry could have made quite a handsome profit selling its fluoride
  23. 23. wastes to industry. This was indeed the hope among some industry analysts, including the authors of the review noted above (Denzinger 1979). However, the US phosphate industry has thus far been unable to take advantage of this market. The principal reason for this failure stems from the fact that fluoride captured in the scrubbers is combined with silica. The resulting silicofluoride complex has, in turn, proved difficult for the industry to separate and purify in an economically-viable process. As it now stands, silicofluoride complexes (hydrofluorosilicic acid & sodium silicofluoride) are of little use to industry. Thus, while US industry continues to satisfy its growing demand for high-grade fluoride chemicals by importing calcium fluoride from abroad (primarily from Mexico, China, and South Africa), the phosphate industry continues dumping large volumes of fluoride into the acidic wastewater ponds that lie at the top of the mountainous waste piles which surround the industry. In 1995, the Tampa Tribune summed up the situation as follows: “The U.S. demand for fluorine, which was 400,000 tons, is expected to jump 25 percent by next year… Even though 600,000 tons of fluorine are contained in the 20 million tons of phosphate rock mined in Florida, the fluorine market has been inaccessible because the fluorine is tied up with silica, a hard, glassy material.” Of course, not all of the phosphate industry’s fluoride waste is disposed of in the ponds. As noted earlier, the phosphate industry has found at least one regular consumer of its silicofluorides: municipal water-treatment facilities. According to recent estimates, the phosphate industry sells approximately 200,000 tons of silicofluorides (hydrofluorosilicic acid & sodium silicofluoride) to US communities each year for use as a water fluoridation agent (Coplan & Masters 2001). Fluoridation: According to Dr. J. William Hirzy, the current Senior Vice-President of EPA Headquarters Union “If this stuff gets out into the air, it’s a pollutant; if it gets into the river, it’s a pollutant; if it gets into the lake it’s a pollutant; but if it goes right into your drinking water system, it’s not a pollutant. That’s amazing… There’s got to be a better way to manage this stuff.” Recent Findings on Silicofluorides Adding to Hirzy’s, and the EPA Union’s, concerns are three recent findings. First and foremost are two recent studies reporting a relationship between water treated with silicofluorides and elevated levels of lead in children’s blood (Masters & Coplan 1999, 2000). The authors of these studies speculate that the silicofluoride complex may increase the uptake of lead (derived from other environmental sources, such as lead paint) into the bloodstream. The second finding is the recent, and quite remarkable concession from the EPA, that despite 50 years of water fluoridation, the EPA has no chronic health studies on silicofluorides. All safety studies on fluoride to date have been conducted using
  24. 24. pharmaceutical-grade sodium fluoride, not industrial-grade silicofluorides. A similar concession has also been obtained from the respective authorities in England. The defense made by agencies promoting water fluoridation, such as the US Centers for Disease Control, to the lack of such studies, is that when the silicofluoride complex is diluted into water, it dissociates into free fluoride ions or other fluoride compounds (e.g. aluminum-fluoride), and thus the treated water, when consumed, will have no remaining silicofluoride residues (Urbansky & Schock, 2000). This argument, while supported by a good deal of theoretical calculation is at odds with a recently obtained and translated PhD dissertation from a German chemist. (Westendorf 1975). According to the dissertation, not only do the silicofluorides not fully dissociate, the remaining silicofluoride complexes could be more potent inhibitors of cholinesterase, an enzyme vital to the functioning of the central nervous system. The third finding is that the silicofluorides, as obtained from the scrubbers of the phosphate industry, contain a wide variety of impurities present in the process water – particularly arsenic and possibly radionuclides. While these impurities occur at low concentrations, especially after dilution into the water, their purposeful addition to water supplies directly violates EPA public health goals. For instance, the EPA’s Maximum Contaminant Level Goal for arsenic, a known human carcinogen, is 0 parts per billion. However, according to the National Sanitation Foundation, the addition of silicofluorides to the water supply will add, on average, about 0.1 to 0.43 ppb, and as much as 1.6 ppb, arsenic to the water. As noted by the Salt Lake Tribune, “Those who had visions of sterile white laboratories when they voted for fluoride weren’t thinking of fluorosilicic acid. Improbable as this sounds, much of it is recovered from the scrubbing solution that scours toxins from smokestacks at phosphate fertilizer plants.” Gypsum Stacks & ‘Slime Ponds’ Fluoride-contaminated wastewater sitting on top of “gypsum stack.”To make 1 pound of commercial fertilizer, the phosphate industry creates 5 pounds of contaminated phosphogypsum slurry (calcium sulfate). This slurry is piped from the processing facilities up into the acidic wastewater ponds that sit atop the mountainous waste piles known as gypsum stacks. According to the EPA, 32 million tons of new gypsum waste is created each year by the phosphate industry in Central Florida alone. (Central Florida is the heart of the US phosphate industry). The EPA estimates that the current stockpile of waste in Central Florida’s gypsum stacks has reached “nearly 1 billion metric tons.” (The average gypsum stack takes up about 135 acres of surface area – equal to about 100 football fields – and can go as high as 200 feet.)
  25. 25. Radiation Hazard It is sort of a misnomer, however, to call these stacks “gypsum” stacks. Indeed, if the stacks were simply gypsum, they probably wouldn’t exist, as gypsum can be readily sold for various purposes (e.g. as a building material). What can’t be readily sold, however, is radioactive gypsum, which is about the only type of gypsum the phosphate industry has to offer. The source of the gypsum’s radioactivity is the presence of uranium, and uranium’s various decay products (i.e. radium), in raw, phosphate ore. As noted by the Sarasota Herald Tribune “there is a natural and unavoidable connection between phosphate mining and radioactive material. It is because phosphate and uranium were laid down at the same time and in the same place by the same geological processes millions of years ago. They go together. Mine phosphate, you get uranium.” Phosphate ore can contain high concentrations of uranium, as evident by this sign at IMC Agrico’s plant in Polk County. While uranium, and its decay-products, naturally occur in phosphate ore, their concentrations in the gypsum waste, after the extraction of soluble phosphate, are up to 60 times greater. The gypsum has therefore been classified as a “Naturally Occurring Radioactive Material“, or NORM waste, although some, including the EPA, have questioned whether this classification understates the problem. According to the Tampa Tribune, the gypsum “is among the most concentrated radioactive waste that comes from natural materials.” It is so concentrated, in fact, that “it can’t be dumped at the one landfill in the country licensed to take only NORM waste.” Thus, according to US News & World Report, the EPA is currently “weighing whether to classify the gypsum stacks as hazardous waste under federal statutes, which would force the industry to provide strict safeguards” (to nearly 1 billion tons of waste). One of EPA’s main concerns with gypsum stacks centers around the fact that radium- 226 breaks down into radon gas. When radon gas is formed, it can become airborne, leading to potentially elevated exposures downwind of the stacks. Such airborne exposures are of particular concern to areas like Progress Village, Florida, where “a new gypsum stack is rising a few hundred yards from a grade school.” According to US News & World Report, there is evidence to suggest cancer rates downwind of the stacks may be elevated: “Some epidemiological studies suggest that lung cancer rates among nonsmoking men in the phosphate region are up to twice as high as the state average. Acute leukemia rates among adults are also double the average. An industry-sponsored
  26. 26. study of male phosphate workers, however, found lung cancer rates no higher than the state average. There is no proof that mine wastes cause cancer, but the evidence is worrisome.” Will radioactive gypsum be added to roads? With the growing realization that gypsum stacks represent a serious environmental threat to Central Florida, both now and for generations to come, the phosphate industry has been looking into ways of reducing the size of the stacks (and the size of their liability.) In an interesting parallel to fluoride, the phosphate industry is looking to turn its gypsum waste into a marketable product: as a potential cover for landfills, as a soil conditioner, and as a base material for roads. As of yet, however, the EPA does not appear willing to relax its rules and lift its ban on commercial uses of gypsum. According to the Tampa Tribune, “EPA’s limit for use is 10 picocuries of radium per gram, well below the levels usually found in the mounds.” A recent statement from the EPA reads: “Only two uses (for the gypsum) are permitted: limited agricultural use and research. Other uses may be proposed, but otherwise the phosphogypsum must be returned to mines or stored in stacks.” Cold War Secrets & Worker Health In Joliet, Illinois, it has only recently come to light that the local phosphate plant had secretly produced some 2 million pounds of uranium for the US government in the years 1952 to 1962. According to local newspaper reports, the cancer rates of people who worked at the plant, especially “Building 55” where the uranium was processed, are unusually high. Today, with the Cold War over, it is becoming clear that workers in the phosphate industry need special protection. According to a report from the European Commission: “Processing and waste handling in the phosphate industry is associated with radiation levels of concern for workers and the public. The level of protection for these groups should be more similar to the level of protection that is state of the art in other industries, particularly the nuclear industry.” Wastewater Issues While the radioactivity of the gypsum stacks has probably been the key health concern of the EPA, it is not the only one. Resting atop the phosphate industry’s gypsum piles are highly-acidic wastewater ponds, littered with toxic contaminants, including fluoride, arsenic, cadmium, chromium, lead, mercury, and the various decay-products of uranium. This
  27. 27. combination of acidity and toxins makes for a poisonous, high-volume, cocktail, which, when leaked into the environment, wreaks havoc to waterways and fish populations. As noted by the St. Petersburg Times, “Spills from these stacks have periodically poisoned the Tampa Bay environs. ” One spill, in 1997, from a now-defunct gypsum stack in Florida, “killed more than a million fish.” “Strike the Alafia River off your list of fishing spots,” wrote one journalist after the spill. “It’s gone, dead as a sewer pipe, killed by the carelessness of yet another phosphate company.” Today, the same gypsum stack which caused this particular spill, is considered by Florida’s Department of Environmental Protection to be “the most serious pollution threat in the state.” That’s because tropical rains over the past couple of years have brought the wastewater to the edge of the stack’s walls. As noted by the Tampa Tribune, “The gypsum mound is near capacity, and a wet spring or a tropical storm could cause a catastrophic spill.” To prevent such a spill, which was all but inevitable, the EPA recently agreed to let Florida pursue “Option Z“: To load 500-600 million gallons of the wastewater onto barges and dump it directly into the Gulf of Mexico. The dumping of the wastewater into the Gulf represents the latest in a series of high-profile embarrasments for Florida’s phosphate industry; one of the most dramatic of which happened on June 15, 1994. On that day, a massive, 15-story sinkhole appeared in the middle of an 80 million ton gypsum stack. The hole was so big that, according to US News & World Report, it “could be as big as 2 million cubic feet, enough to swallow 400 railroad boxcars. Local wags call it Disney World’s newest attraction — ‘Journey to the Center of the Earth.’” But, as US News noted, “there’s nothing amusing about it. The cave-in dumped 4 million to 6 million cubic feet of toxic and radioactive gypsum and waste water into the Floridan aquifer, which provides 90 percent of the state’s drinking water.” ( an-environmental-overview-fluoride-is-poison/) Thus it can be seen that processing Rock phosphate into super phosphates involves heavy environmental pollution and is becoming a threat to Livestock and humans.
  28. 28. NNNEEEEEEDDD FFFOOORRR AAA NNNOOOVVVEEELLL PPPHHHOOOSSSPPPHHHOOORRRUUUSSS NNNUUUTTTRRRIIIEEENNNTTT SSSUUUPPPPPPLLLEEEMMMEEENNNTTTAAATTTIIIOOONNN Low utilization of native-P by crops and high fixation of applied P had been a major concern in crop production for over three decades. Different approaches viz. phosphorus solubilizing bacteria (PSB), phosphatase and phytase producing fungi (PPF), organic acid producing microorganisms, and VAM have been tried in past to address these problems. But success of these phosphorus mobilizing microorganisms (PMM) had been limited for two reasons (a) Low soil organic carbon (SOC) which limit the energy supply to PMM (b) High evaporation from surface soils which adversely affect the survivability of PMM. (,-99,746) NOW WE PROPOSE 1. TO REDUCE LEVEL OF USAGE OF PHOSPHATIC FERTILIZERS AND THUS MINIMIZE PRODUCTION OF PHOSPHATIC FERTILIZERS 2. TO INSTILL MORE BIOAVAILABLE PROTEINATED PHOSPHOROUS AND THUS EVEN REDUCE RESIDUAL PHOSPHORUS LEACHATES INTO SURFACE WATERS 3. TO REDUCE QUANTITY OF LITTER WHEN USED IN ANIMALS
  29. 29. HHHOOOWWW CCCAAANNN TTTHHHIIISSS BBBEEE AAACCCHHHIIIEEEVVVEEEDDD??? Plants exude about 25 to 30% of the photosynthates through roots. These exudates consist of low molecular weight amino acids, amino sugars, organic acids and polysaccharides and can provide energy to PMM and C skeleton for synthesis of exo-polysaccharides. Any attempt to increase proportion of root exudates would logically result in yield reduction; therefore, we propose to increase photosynthesis in crop plants to achieve higher root exudates. Nano-particles of Mg, Zn, Fe and P are the structural component of enzymes (phosphatases and phytase), polysaccharides and chlorophyll. They are known to stabilize the enzyme complexes in plants. We aim on utilizing this property for increasing photosynthesis that would most likely lead to higher exudation which in turn would increase the energy supply and supply of C skeleton compounds to PMM and exo-polysaccharide producing micro-organisms. This approach would enable in breaking of existing barriers in utilization of native P and reduce dependence on imported P fertilizers. Most of the P in soil is bound as highly stable Ca-P, Fe-P, Al-P and as plant unavailable inorganic form besides C-O-P ester bond in organic form. These bonds can be solubilized/hydrolyzed by phosphatases, phytase enzymes and organic acid produced by microorganisms viz. phosphorus solubilizing bacteria, phosphatase and phytase producing microorganisms and arbuscular mycorrhizal fungi through biochemical reactions. But this biochemical process is energy intensive. Total energy availability in arid soils is low due to low SOC. As a consequence the population, survivability and efficacy of phosphorus mobilizing microorganisms (PSM) in soil is low. Utilization efficiency of phosphatic fertilizers is very low due to their inversion to insoluble forms in general and it is further aggravated in arid soils by higher concentration of silicic acid and calcium carbonate. We propose to synthesize nano-particles of rock phosphate and use them as fertilizer by direct application on plant surface. This would avoid contact of P with soil to avert inversion and increase utilization efficiency of fertilizer P by crops. Moreover, there would be no competition with silicic acid and also no fixation by calcium. (,-99,746)
  30. 30. NOW WE OFFER COLION_P IONISED PHOSPHOROUS EMBEDDED IN A MATRIX OF COLLOIDAL AMINOACID LIKE L LYSINE, WHICH IS CONSIDERED AS AN ESSENTIAL AMINOACID. COLION_P is totally bioavailable and enters into plant system as a bioencapsulated molecule in whole and results in no antagonisms. Organic P content in COLION_P can replace ten folds inorganic P supplements. MMMOOODDDEEE OOOFFF AAACCCTTTIIIOOONNN OOOFFF CCCOOOLLLIIIOOONNN___PPP Natural Ionised Phosphorus and Colloidal Protein successfully combined with a biopolymer. This blend has been delicately handled to ensure the full benefit of a boost to metabolism of high performance ruminants, poultry, fish, prawn, agricultural crops etc, in a safe naturally occurring manner. This product is totally bioassimable as a whole without break up and will also improve the performance of the microflora.
  31. 31. CCCOOOLLLIIIOOONNN___PPP COLION_P is a non-phosphite phosphorous nutrient formulation to help harvest the best crop. COLION_P safely replaces Use of Dicalcium phosphate and Phytase in animal feeds. In Agriculture, COLION_P can be conveniently applied through the drippers at early stages of crops and through the leaves ( foliar ) during the fruiting and later stages of growth to produce the best quality crop with higher yields. In Animals it can be safely used either in feed or in drinking water. COLION_P contains Phosphorous, Metabolites of Phosphorous Solubilising Bacteria, Phytase and Phosphatase Enzymes, which is an unique combination. When available P is considered  COLION_P replaces inorganic phosphorus sources like rock Phosphate and Superphosphate.  Organic phosphorous content of 1 L COLION_P can replace 15 Kg Superphosphate. Metabolites of the Microbes and enzymes impart efficiency to the plants to uptake the insoluble Phosphorus available in the soil. STUDY CONDUCTED Combinations of trisodium phosphate with boric acid and sodium humate gave superior results as compared to superphosphate (maximum productivity 74.7 t/ha). Use of trisodium phosphate also obtained beetroot with the highest sugar (9.7%) and the lowest nitrate (1232 mg/kg) contents. (
  33. 33. RECOMMENDED CROPS Corn, Soy bean, Fruits, Vegetables, Rice, Sugar cane, Wheat, Cotton, Tobacco etc RECOMMENDED ANIMALS POULTRY, CATTLE, SHEEP, FISH AND PRAWN RECOMMENDED DOSE: IN AGRICULTURE As P Source: 6.66 L COLION_P can replace 100 Kg Single super phosphate. 8 to 16 ml per liter of water for spraying/ Sprinkler/Drip; first during preparation of the soil before sowing; Then when the crop is 1-2 weeks old; Again one week before when it is going to flowering, Lastly 1-2 weeks before harvesting. In the cases of diseases like downy mildew of grapes, fruit rot, Root Rot & citrus Gummosis, Late blight of Tomato etc; 20- 30 ml per L of Water for spraying/ Sprinkler/Drip. Other key nutrients like all water-soluble fertilizers, nitrogen and trace elements can be mixed with COLION_P except for calcium fertilizers and concentrated magnesium solutions. In hydroponic systems, it should normally be added to the B tank along with the sulphates and trace elements. COLION_P has a buffering effect which will help stabilize the pH of the solution at around 5.5. IN ANIMAL FEEDS: 1 L per MT Feed regularly replacing 10 Kg DCP of 18% P, and 50g PHYTASE of 10000 IU/g Or 0.5 ml per 1 L in drinking water to replace 10 Kg DCP of 18% P, and 50g PHYTASE of 10000 IU/g in feed
  34. 34. PROXIMATE ANALYSIS: Phosphorous as P: 0.18 % Min Phosphorous as P2O5: 0.382 % Min Chloride as Cl : 0.01%max Iron(as Fe): 0.0005%max Arsenic(as As): 0.0005%max. pH: 4.35-4.85 Suitable pH Buffers PACKING: 25 L REFERENCES:  Barrett, SR, BL Shearer and GE Hardy (2002). Australian J. Bot.  Lucas, RE, DD Warncke and VA Thorpe (1979). Agron. J. 71, 1063-1065.  McDonald, AE, BR Grant and WC Plaxton (2001). J. Plant Nutr. 24, 1505- 1519.  Mitchell, C and J Adam (2004). Alabama Coop. Ext. Sys., S-04-04. May 2004.  Wells, KL, JE Dollaride and RE Mundell (2000). Comm. Soil Sci Plant Anal. 31, 2707-2715  Bellack E, Baker RJ. (1970). Fluoridation chemicals – the supply picture. Journal of the American Water Works Association 62: 223-224.  Coplan MJ, Masters RD. (2001). Silicofluorides and fluoridation. Fluoride 34(3):161- 220.  Denzinger HF, et al. (1979). Fluorine recovery in the fertilizer industry – a review. Phosphorus & Potassium Sept/Oct: 33-39.  Ender F. (1969). “The effect of air pollution on animals.” pp. 245-254. In: Air Pollution – Proceedings of the First European Congress on the Influence of Air Pollution on Plants and Animals, Wageningen, April 22 to 27, 1968. Centre for Agricultural Publishing & Documentation, Wageningen.  Hirzy JW. (2000). Video-taped interview with Dr. J. William Hirzy, Senior Vice President, EPA Headquarters Union. Interview by Michael Connett. July 3.  Hodge HC, Smith FA. (1977). Occupational fluoride exposure. Journal of Occupational Medicine 19: 12-39.  Lillie RJ. (1970). Air Pollutants Affecting the Performance of Domestic Animals: A Literature Review. U.S. Dept. of Agriculture. Agricultural Handbook No. 380. Washington D.C.  Masters R, et al. (2000). Association of Silicofluoride Treated Water with Elevated Blood Lead. Neurotoxicology 21(6): 1091-1099.
  35. 35.  Masters RD, Coplan M. (1999). Water treatment with Silicofluorides and Lead Toxicity. International Journal of Environmental Studies 56: 435-449.  Shupe JL. (1970). Fluorine toxicosis and industry. American Industrial Hygiene Association Journal 31: 240-247.  Urbansky ET, Schock MR. (2000). Can Fluoridation Affect Water Lead(II) Levels and Lead(II) Neurotoxicity? United States Environmental Protection Agency (EPA), Office of Research and Development, National Risk Management Research Laboratory, Water Supply and Water Resources Division, Cincinnati, Ohio.  Weinstein LH. (1983). “Effects of Fluorides on Plants and Plant Communities: An Overview.” pp. 53-59. In: Shupe JL, Peterson HB, Leone NC, (Eds). Fluorides: Effects on Vegetation, Animals, and Humans. Paragon Press. Salt Lake City, Utah.  Westendorf J. (1975). The kinetics of acetylcholinesterase inhibition and the influence of fluoride and fluoride complexes on the permeability of erythrocyte membranes. Ph.D. Dissertation in Chemistry, University of Hamburg, Germany.