What is a Fertilizer?

Fertilizer is a substance added to soil to improve plants' growth and yield. First used by ancient farmers, fertilizer technology developed significantly as the chemical needs of growing plants were discovered. Modern synthetic fertilizers are composed mainly of nitrogen, phosphorous, and potassium compounds with secondary nutrients added. The use of synthetic fertilizers has significantly improved the quality and quantity of the food available today, although their long-term use is debated by environmentalists. Like all living organisms, plants are made up of cells. Within these cells occur numerous metabolic chemical reactions that are responsible for growth and reproduction. Since plants do not eat food like animals, they depend on nutrients in the soil to provide the basic chemicals for these metabolic reactions. The supply of these components in soil is limited, however, and as plants are harvested, it dwindles, causing a reduction in the quality and yield of plants.

Why is Fertilizer important?

Fertilizers replace the chemical components that are taken from the soil by growing plants. However, they are also designed to improve the growing potential of soil, and fertilizers can create a better growing environment than natural soil. They can also be tailored to suit the type of crop that is being grown. Typically, fertilizers are composed of nitrogen, phosphorus, and potassium compounds. They also contain trace elements that improve the growth of plants. The primary components in fertilizers are nutrients which are vital for plant growth. Plants use nitrogen in the synthesis of proteins, nucleic acids, and hormones. When plants are nitrogen deficient, they are marked by reduced growth and yellowing of leaves. Plants also need phosphorus, a component of nucleic acids, phospholipids, and several proteins. It is also necessary to provide the energy to drive metabolic chemical reactions. Without enough phosphorus, plant growth is reduced. Potassium is another major substance that plants get from the soil. It is used in protein synthesis and other key plant processes. Yellowing, spots of dead tissue, and weak stems and roots are all indicative of plants that lack enough potassium. Calcium, magnesium, and sulfur are also important materials in plant growth. They are only included in fertilizers in small amounts, however, since most soils naturally contain enough of these components. Other materials are needed in relatively small amounts for plant growth. These micronutrients include iron, chlorine, copper, manganese, zinc, molybdenum, and boron, which primarily function as cofactors in enzymatic reactions. While they may be present in small amounts, these compounds are no less important to growth, and without them plants can die. Many different substances are used to provide the essential nutrients needed for an effective fertilizer. These compounds can be mined or isolated from naturally occurring sources. Examples include sodium nitrate, seaweed, bones, guano, potash, and phosphate rock. Compounds can also be chemically synthesized from basic raw materials. These would include such things as ammonia, urea, nitric acid, and ammonium phosphate. Since these compounds exist in a number of physical states, fertilizers can be sold as solids, liquids, or slurries.

Types of Fertilizer
(1) Inorganic Fertilizer: Liquid hydroponic nutrients are made from inorganic materials to speed their release into indoor garden and make them easier to mix with water. These hydroponic nutrient solutions contain the vital macronutrients nitrogen, phosphorus, and potassium (NPK) in blends designed for either vegetative growth or blooming. Supplemental inorganic fertilizers are also available to add plant micronutrients to your hydroponic system. Inorganic fertilizers are usually quick-release formulas making nutrients rapidly available to plants. Inorganic fertilizers are safe to use, however, because it is quick-releasing, salts can build up fast, damaging soil (Soil applications), pumps and air stones used in hydroponics application. For example: Ammonia Ammonium fertilizers Nitrate and Ammonium fertilizers

(2) Organic Fertilizer Organic fertilizers include naturally occurring organic materials, For example: manure, worm castings, compost, seaweed, guano or Naturally occurring mineral deposits (e.g. saltpeter).

Organic nutrients increase the abundance of soil organisms by providing organic matter and micronutrients for organisms such as fungal mycorrhiza, (which aid plants in absorbing nutrients), and can drastically reduce external inputs of pesticides, energy and fertilizer, at the cost of decreased yield.

Fertilizer Grading
The analysis or grade refers to the minimum amounts of N, P 2O5 and K20 in the fertilizer. A 10-10-10 fertilizer would contain 10 percent nitrogen (N), 10 percent P2O5 equivalent and 10 percent K2O equivalent. In 50 pounds of 10-10-10, there are 5 pounds of N, 5 pounds of P2O5 equivalent and 5 pounds of K2O equivalent.

Nitrogenous Fertilizer
According to the manner in which their nitrogen is combined with other elements, called as Nitrogenous Fertilizer. It provides nitrogen for plants to make plant proteins, Necessary for growth and repair of plant cells. It promotes plant growth and increase crop yields. Most plants are unable to make use of atmospheric nitrogen (79%) directly. Plants get nitrogen supply by absorbing soluble nitrogen compounds from the soil Examples: ammonium nitrate, ammonium sulfate, urea CO (NH2)2

The nitrogenous fertilizers are divided into 4 groups

Ammonia (82-0-0)
Used as an applied fertilizer or as a building block for other fertilizer products. Stored as a liquid under pressure or refrigerated, it becomes a gas when exposed to air and is injected into the soil.

Ammonium fertilizers (NH4+)

Ammonium fertilizers are soluble in water and, as such, absorbed on the soil colloids and thus protected from being washed away by run off or by leaching. Some crops like rice, sugarcane, tuber crop, seedlings directly utilize ammonium form of these fertilizers. The absorbed ammonium ions on soil collections are transformed to nitrate slowly and taken up by most of the crops. They are acidic in their residual effect in soil. Following are the ammonium fertilizers.

Fertilizer Ammonium Sulphate (NH4)2SO4 Ammonium Chloride NH4Cl Ammonium phosphate-NH4 (H2PO4) Anhydrous ammonia -NH3 Ammonia Solution -NH3 in water

% of Nitrogen 20.6%N 25%N 20%N 82%N 20 to 25%N

Nitrate and Ammonium fertilizers

These fertilizers contain nitrogen in both nitrate (NO 3 ) and ammonium forms (NH4 ). The nitrate nitrogen is readily available to plants for immediate need, whereas ammonium nitrogen becomes available to plants at a later stage, when it is transformed by microbiological process to nitrate. They are soluble in water and suitable for most of the crops and soils. They are acidic in its residual effect.
+

Fertilizer Ammonium nitrate-NH4NO3 Calcium Ammonium Nitrate (CAN)-Ca(No3) 2NH4NO3 Ammonium Sulphate Nitrate (ASN)-(NH4) 2SO4NH4NO3

% of Nitrogen 33 to 34%N 25%N

26%N

Amide Fertilizers (NH2 or CN2):

A solid nitrogen product typically applied in granular form. It can be combined with ammonium nitrate and dissolved in water to make liquid nitrogen fertilizer known as urea ammonium nitrate or UAN solution. These fertilizers contains nitrogen in organic compounds as amideNH2 or ---- CN 2 , not directly available to plants, as such , but quickly converted by soil microbes to ammoniacal and nitrate form and then utilized. Amide fertilizers are.

Fertilizer Urea CO(NH2) 2 Calcium Cyanamid CaCN2

% of Nitrogen 46%N 21%N

Manufacturing Processes

Ammonia (NH3)
Ammonia is an intermediate product in the manufacture of nitrogenous fertilizers. It is also used for direct application to the soil and in aqua condition with solutions of other nitrogenous fertilizers like ammonium nitrate and/or urea. Besides these, ammonia finds application in the production of nitric acid, soda ash, cleaning agents, leather tanning, petroleum refining, pulp & paper industry, textiles, refrigeration, rubber & synthetic resin industries, explosives and food & beverage industries. Melting point 77.7C, Boiling point 33.4C, Colorless gas with a penetrating, Produces a smothering sensation when inhaled, Soluble in water, Burns with a greenish yellow flame

Raw materials used Ammonia is produced by the reaction between nitrogen (N2) and hydrogen (H2) N2 + 3 H2 ------> 2 NH3 Source of Nitrogen is atmospheric air and following hydrocarbons are generally used as the source of hydrogen: a) Natural gas b) Naphtha c) Heavy Oil Other sources of hydrogen which were used earlier for manufacture of Ammonia, are: a) Semi-water gas made by gasification of coke/ coal with steam. b) Hydrogen produced by electrolysis of water. c) By product Hydrogen from chlorine production. Purified water is used as feed stock in electrolysis process. Potassium hydroxide is added to increase conductivity, but it does not participate in the reaction.
+

Reduction at cathode: 2 H (aq) + 2e H2(g) Anode (oxidation): 2 H2O(l) O2(g) + 4 H (aq) + 4e H2O -----> H2 + O2 Hydrogen thus obtained is mixed with required nitrogen from the air separation plant to get synthesis mixture. Electrolysis process is very energy intensive process. Typical power consumption is 4.3 KWH/m3 of hydrogen, which corresponds to about 8600 KWH/MT of ammonia. Additional energy is required for the air separation plant to produce nitrogen. Energy is also required for compression of Hydrogen & nitrogen and recirculation of loop gases.
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The total energy requirement is 10,200 KWH/MT of ammonia (8.8 Gcal/MT). The plants based on this process are located where low cost hydro-electricity is available.

The Haber process

Invented in 1908 by Fritz Haber. Originally used to make explosives. Main source of ammonia to make nitrogen fertilizers. The Haber Process combines nitrogen from the air with hydrogen derived mainly from natural gas (methane) into ammonia. The reaction is reversible and the production of ammonia is exothermic.

N2 (g) + 3 H2 (g) 2 NH3 (g) (H = 92.22 kJmol1)

Reactions that can go either direction forward and backward reactions take place at the same time. Do not go into completion. Reactions achieve equilibrium. [equilibrium is achieved when amounts of reactants and products no longer change]. A mixture of reactants and products at the end of the reaction. Amounts of reactants and products at equilibrium can be changed by altering conditions [e.g. temperature and pressure]

Percentage of ammonia obtained by at different temperature.

Effect of conditions on the yield of ammonia . Temperature A lower temperature increases the yield of ammonia. However, a lower temperature also results in a slower reaction Pressure A greater pressure increases the yield of ammonia, as well as the rate of reaction. However, maintaining higher pressure is costly and involves a safety risk Conditions for Haber process

N2 (g) + 3 H2 (g) 2 NH3 (g) (H = 92.22 kJmol )

Temperature of 450 C Pressure of 250 atm. Presence of iron catalyst for maximum yield of ammonia.

2. Ammonium Fertilizer
Ammonium Sulfate
Ammonium sulfate, (NH4)2SO4, is an inorganic salt with a number of commercial uses. The most common use is as a soil fertilizer. It contains 21% nitrogen as ammonium cations, and 24% sulfur as sulfate anions. In fertilizer the purpose of the sulfate is to reduce the soil pH

Uses
1. It is used largely as an artificial fertilizer for alkaline soils. In the soil the ammonium ion is released and forms a small amount of acid, lowering the pH balance of the soil , while contributing essential nitrogen for plant growth. 2. It is also used as an agricultural spray adjuvant for water soluble insecticides, herbicides, and fungicides. There it functions to bind iron and calcium cations that are present in both well water and plant cells. It is particularly effective as an adjuvant for 2,4-D (amine), glyphosate, and glufosinate herbicides. 3. It is also used in the preparation of other ammonium salts. 4. In biochemistry, ammonium sulfate precipitation is a common method for purifying proteins by precipitation. As such, ammonium sulfate is also listed as an ingredient for many United States vaccines per the Center for Disease Control.

5. Ammonium sulfate is also a food additive.

Preparation
Ammonium sulfate is made by reacting synthetic ammonia (or by-product ammonia from coke-ovens) with sulfuric acid 2 NH3 + H2SO4 (NH4)2SO4 A mixture of ammonia gas and water vapor is introduced into a reactor that contains a saturated solution of ammonium sulfate and about 2 to 4% of free sulfuric acid at 60 C. Concentrated sulfuric acid is added to keep the solution acidic, and to retain its level of free acid. The heat of reaction keeps reactor temperature at 60 C. Dry, powdered ammonium sulfate may be formed by spraying sulfuric acid into a reaction chamber filled with ammonia gas. The heat of reaction evaporates all water present in the system, forming a powdery salt. Ammonium sulfate also is manufactured from gypsum (CaSO42H2O). Finely divided gypsum is added to an ammonium carbonate solution. Calcium carbonate precipitates out, leaving ammonium sulfate in the solution. (NH4)2CO3 + CaSO4 (NH4)2SO4 + CaCO3

Ammonium Chloride Ammonium chloride NH4Cl is an inorganic compound with the formula NH4Cl. It is a white crystalline salt that is highly soluble in water. Solutions of ammonium chloride are mildly acidic. Sal ammoniac is a name of natural, mineralogical form of ammonium chloride. In biological applications ammonium chloride serves as a nitrogen source and is used in fertilizers, as a feed supplement for cattle and as an ingredient in nutritive media for yeast microbiological organisms. Uses Ammonium chloride is used to produce low temperatures in cooling baths. For example, the zero point of Fahrenheit temperature scale is determined by placing the thermometer in a mixture of ice, water, and ammonium chloride. Ammonium chloride solutions with ammonia are used as buffer solutions. Pyrotechnics Ammonium chloride is an ingredient in fireworks and safety and contact explosives. Textile and leather Ammonium chloride is used in the textile and leather industry in dyeing, tanning textile printing and to luster cotton.

Metalwork Ammonium chloride is used as a flux in preparing metals to be tin coated, galvanized or soldered. It works as a flux by cleaning the surface of workpieces by reacting with the metal oxides at the surface to form a volatile metal chloride. For this purpose, it is sold in blocks at hardware stores for use in cleaning the tip of a soldering iron and can also be included in solder as flux. Food In several countries ammonium chloride is known as sal ammoniac and used as food additive. The E number for ammonium chloride used as a food additive is E510.

Preparation Ammonium chloride is prepared commercially by combining ammonia (NH3) with either hydrogen [3] chloride or hydrochloric acid: NH3 + HCl NH4Cl This reaction can occur if poorly sealed bottles of household ammonia (ammonium hydroxide) and hydrochloric acid are stored in close proximity.

3. Nitrate and Ammonium fertilizers This is done using anhydrous ammonia gas and concentrated nitric acid This reaction is violent and very exothermic. After the solution is formed, typically at about 83% concentration, The excess water is evaporated to an ammonium nitrate (AN) content of 95% 99.9% concentration (AN melt), depending on grade. The AN melt is then made into "prills" ,small beads in a spray tower, or into granules by spraying and tumbling in a rotating drum. The prills or granules may be further dried, cooled, and then coated to prevent caking. These prills or granules are the typical AN products in commerce.

Prilling and Granulation Prilling refers to the formation of granules by the solidification of droplets of fertilizer materials. Granulation is a more general term and refers to techniques using processes such as agglomeration, accretion, or crushing to make a granular fertilizer. There are currently no plants in Europe which use either a crushing or a compaction/flaking technique to make ammonium nitrate or CAN. One process uses prills as the feed to a layering-type granulation unit to produce a larger (fattened) granule when compared with the prilled feed. The prilling technique is used in many plants for the production of ammonium nitrate and in some plants for CAN. Granulation of ammonium nitrate may be performed in a dedicated plant, or in one which can also produce CAN. Dedicated CAN plants exist where the CAN is granulated. CAN may also be manufactured in a plant which produces NPK fertilizers.

3.Amide Fertilizer Urea:

It is solid, colorless, and odorless It is highly soluble in water and non-toxic. Dissolved in water it is neither acidic nor alkaline. The body uses it in many processes, most notably nitrogen excretion.

More than 90% of world production of urea is destined for use as a nitrogen-release fertilizer. Urea has the highest nitrogen content of all solid nitrogenous fertilizers in common use. Therefore, it has the lowest transportation costs per unit of nitrogen nutrient. The standard crop nutrient rating of urea is 46-0-0 Many soil bacteria possess the enzyme, urease, which catalyzes the conversion of the urea molecule to two ammonia molecules and one carbon dioxide molecule, thus urea fertilizers are very rapidly transformed to the ammonium form in soils. Among soil bacteria known to carry urease, some ammonia-oxidizing bacteria (AOB), such as species of Nitrosomonas are also able to assimilate the carbon dioxide released by the reaction to make biomass via the Calvin Cycle, and harvest energy by oxidizing ammonia (the other product of urease) to nitrite, a process termed nitrification. Nitriteoxidizing bacteria, especially, Nitrobacter, oxidize nitrite to nitrate, which is extremely mobile in soils and is a major cause of water pollution from agriculture. Ammonia and nitrate are readily absorbed by plants, and are the dominant sources of nitrogen for plant growth. Urea is also used in many multicomponent solid fertilizer formulations. Urea is highly soluble in water and is, therefore, also very suitable for use in fertilizer solutions (in combination with ammonium nitrate: UAN), e.g., in 'foliar feed' fertilizers. For fertilizer use, granules are preferred over prills because of their narrower particle size distribution which is an advantage for mechanical application.

Urea is usually spread at rates of between 40 and 300 kg/ha but rates vary. Smaller applications incur lower losses due to leaching.urea is often spread just before, or during rain to minimize losses from volatilization (process wherein nitrogen is lost to the atmosphere as ammonia gas). Urea is not compatible with other fertilizers. Industrial methods For use in industry, urea is produced from synthetic ammonia and carbon dioxide. Large quantities of carbon dioxide are produced during the manufacture of ammonia from coal or from hydrocarbons such as natural gas and petroleum-derived raw materials. Such point sources of CO2 facilitate direct synthesis of urea. The basic process, developed in 1922, is also called the Bosch-Meiser urea process after its discoverers. The various urea processes are characterized by the conditions under which urea formation takes place and the way in which unconverted reactants are further processed. The process consists of two main equilibrium reactions, with incomplete conversion of the reactants. The first is an exothermic reaction of liquid ammonia with dry ice to form ammonium carbamate (H2N-COONH4) 2 NH3 + CO2 H2N-COONH4 () The second is an endothermic decomposition of ammonium carbamate into urea and water: H2N-COONH4 (NH2)2CO + H2O Both reactions combined are exothermic. Unconverted reactants can be used for the manufacture of other products, for example ammonium nitrate or sulfate, or they can be recycled for complete conversion to urea in a total-recycle process. Urea can be produced as prills, granules, pellets, crystals, and solutions. Solid urea is marketed as prills or granules. The advantage of prills is that, in general, they can be produced more cheaply than granules. Properties such as impact strength, crushing strength, and free-flowing behaviour are, in particular, important in product handling, storage, and bulk transportation. Typical impurities in the production are biuret and isocyanic acid: 2 NH2CONH2 H2NCONHCONH2 + NH3 NH2CONH2 HNCO + NH3 The biuret content is a serious concern because it is often toxic to the very plants that are to be fertilized. Urea is classified on the basis of its biuret content.

Negative environmental effects On organism..

Some medical studies have suggested that certain disorders of the urinary and kidney systems are a result of excessive nitrates in drinking water. It is also thought that this is particularly harmful for babies and could even be potentially carcinogenic. It loses its ability to store oxygen Nitrosamines are another potential byproduct of the nitrates in fertilizer. They are the result of a natural chemical reaction of nitrates. Nitrosamines have been shown to cause tumors in laboratory animals, feeding that has a same result could happen in humans. But there has no study that shows a link between fertilizer use and human tumors.

On water quality

Eutrophication
Eutrophication is the movement of a water bodys trophic status in the direction of more plant biomass, by the addition of artificial or natural substances, such as nitrates and phosphates, through fertilizers or sewage, to an aquatic system. In other terms, it is the "bloom" or great increase of phytoplankton in a water body. Negative environmental effects include hypoxia, the depletion of oxygen in the water, which induces reductions in specific fish and other animal populations. Other species (such as Nemopilema nomurai jellyfish in Japanese waters) may experience an increase in population that negatively affects other species The main effects caused by eutrophication can be summarized as follows 1. Species diversity decreases and the dominant biota changes 2. Plant and animal biomass increase 3. Turbidity increases 4. Rate of sedimentation increases, shortening the lifespan of the lake 5. Anoxic conditions may develop Because of the high concentration of organisms in a eutrophic system, there is often a lot of competition for resources and predator pressure. This high degree of competition and the sometimeshigh chemical or physical stress make high the struggle for survival in eutrophic systems. As a result the diversity of organisms is lower in eutrophic than in oligotrophic systems.

Blue baby syndrome

Blue baby syndrome can also be caused by Methemoglobinemia. It is believed to be caused by high nitrate contamination in ground water resulting in decreased oxygen carrying capacity of hemoglobin in babies leading to death. The groundwater is thought to be contaminated by leaching of nitrate generated from fertilizer used in agricultural lands and waste dumpst may also be related to some pesticides (DDT, PCBs etc), which cause ecotoxicological problems in the food chains of living organisms, increasing BOD, which kills aquatic animals

On Atmosphere Green house effect

trapping of heat near Earths surface by gases in the atmosphere Particularly carbon dioxide.

Green house effect can cause to global warming.

Effect of Global warming

Disrupt delicate thermal balance.

Could cause glaciers and ice caps melt. Sea level rises and coastal area would be flooded.

The EU-27 countries currently contribute9.2% of total GHG emissions but thepercentage is declining due to better farmpractice and fertilizer production techniques.CO2 emissions from land use change are notlarge in Europe and the most relevant GHGsare nitrous oxide (N2O) from soil appliednitrogen and fertilizer production, and methane (CH4) from cattle.N2O emitted from the soil represents some 50% of total agricultural emissions. Even when it is not being farmed, the soilnaturally releases GHGs. N2O is generated as a by-product of microbiological activities that convert ammonium into nitrate (nitrification) or nitrate into nitrogen gas N2 (dinitrification). Both processes are influenced and controlled by environmental conditions. They are independent of the origin of the nitrogen, whether from organic or mineral fertilizers, or soil organic matter. Depletion of ozone in the stratosphere Stratospheric ozone can destroy by nitrogen oxides, generally denote as NO X (Example of NOX are NO and NO2.). These compound come from as the agriculture byproduct. Solar radiation decomposes of other nitrogen oxide to nitric oxide, which participates in the destruction of ozone as follows; O NO + O
2 3

O +O
2

NO + O
2

NO + O overall 2O
2 2

NO + O 3O

NO also react with chlorine monoxide to form chlorine nitrate NO + ClO ClONO
2

Chlorine nitrate is relatively stable and serve as Chlorine reservoir. Which plays a role in the depletion of the stratospheric ozone over the North and South Poles.

Acid rain
Acid rain is a rain or any other form of precipitation that is unusually acidic, meaning that it possesses elevated levels of hydrogen ions (low pH). It can have harmful effects on plants, aquatic animals, and infrastructure through the process of wet deposition. Acid rain is caused by emissions of sulfur dioxide and nitrogen oxides which react with the water molecules in the atmosphere to produce acids. That gases coming from N and S fertilizes decomposed by soil microorganisms and aquatic microorganisms . Nitrogen oxides can also be produced naturally by lightning strikes and sulfur dioxide is produced by volcanic eruptions.The chemicals found in acid rain can cause paint to peel and stone statues to begin to appear old and worn down, which reduces their value and beauty

Every year acid rain causes hundreds of millions of dollars worth damage to stone building and statues throughout the world. acid rain is also toxic to vegetation and aquatic life. Many welldocumented cases show dramatically how acid rain has destroyed agriculture and forest lands and killed aquatic organisms.