SES-504(Soil Fertility & Fertilizers Use)

Topic:
Ammonia Volatilization & Its Impact on Water and Air

Submitted To:
Dr.Rai Mukarram Ali Tahir

Submitted By:
Muhammad Irfan BAGF09M008

Department:
Soil & Environmental Sciences, University College of Agriculture, University of Sargodha.

Ammonia volatilization
What is ammonia?
Ammonia is one of the most widely produced chemical. In pure form, it is known as anhydrous ammonia. It is essential in the body as a building block for making proteins and other complex molecules. It is manufactured from nitrogen and hydrogen or is produced from coal gas. In nature, ammonia is formed by the action of bacteria on proteins and urea. It is also produced when plants, and animal wastes decay. The formula for ammonia, NH3, means it consists of one atom of nitrogen and three atoms of hydrogen. Ammonia is rich in nitrogen so it makes an excellent fertilizer. In fact, ammonium salts are a major source of nitrogen for fertilizers

Volatilization of ammonia:
Ammonia is volatilized readily from soil under a number of conditions. Losses are general negligible from soils with pH less than 7 unless there is free ammonia to raise the pH locally. Losses increase with the increase in pH and temperature, and greater in soils having low exchange capacity. The escape of ammonia increases as the soil dries, especially if the ammonia is near the surface. Under submerged conditions, soil nitrate may be reduced to ammonia which may be lost under alkaline conditions. NH4+ NH3 + H+

If pH and temperature can be kept low, little potential exists for NH3 volatilization. At pH 7.5, less than 7% of the ammoniacal N is actually in the form of NH 3 over the range of temperatures likely for field conditions.

Ammonia volatilization from urea:

Urea (N: P: K, 46-0-0) accounts for more than fifty percent of the worlds nitrogenous fertilizers. It is found in granular or prill form, which allows urea to be easily stored, transported and applied in agricultural settings. It is also the cheapest form of granular nitrogen fertilizer. Since urea is not an oxidizer at standard temperature and pressure, it is safer to handle and less of a security risk than other common nitrogen fertilizers, such as ammonium nitrate.

Breakdown of urea:
For plants to absorb nitrogen from urea it must first be broken down:

Urease is a naturally occurring enzyme that catalyzes the hydrolysis of urea to unstable carbamic acid. Rapid decomposition of carbamic acid occurs without enzyme catalysis to form

ammonia and carbon dioxide. The ammonia will likely escape to the atmosphere unless it reacts with water to form ammonium (NH4+) according to the following reaction:

This is important because ammonium is a plant available source of nitrogen while ammonia is not. Additionally, the formation of the hydroxide ion may cause soils around the applied urea particle to have a pH around 9.0 which increases ammonia volatilization. This area is also highly toxic due to elevated ammonia concentration for several hours so it is recommended that urea based fertilizers not be applied or banded with planted seed at a rate that exceeds 10-20 kg/ha, depending on the crop species. It is important that there is adequate moisture because up to thirty percent of the available nitrogen can be lost through atmospheric volatilization within seventy-two hours of application.

Sources of Ammonia:
1. Agricultural activities (livestock production and fertilizer application) have been identified as the major sources of atmospheric ammonia emissions, followed by biomass burning. Within agricultural activities, ammonia emissions into the atmosphere occur primarily from livestock buildings, open feedlots, manure storage facilities, during manure handling and treatment and when manure is applied on land. 2. Ammonia in livestock facilities results primarily from the breakdown of urea by the enzyme urease. In most livestock, urea is only present in the urine while urease is present in the feces. 3. In poultry, urease is excreted with uric acid in the feces. 4. Ammonia volatilization (gassing off) decreases the nutrient value of manure and results in a significant loss of its nitrogen. It also has a negative effect on the environment, such as soil acidification and eutrophication (deprivation of oxygen). Ammonia lost to the atmosphere combines with nitric acid to form airborne nitrate particles that have serious effects on human health and can cause visibility impairment.

Factors Affecting Volatilization:

Significant volatilization of ammonia can occur within the first 24 hours after the land application of manure. More than 50 per cent of the total emission of ammonia can occur within the first six hours after application. Ammonia volatilization is highly dependent on manure management techniques and environmental factors. 1. Manure type and characteristics: Manure characteristics such as total nitrogen (TN), ammonium nitrogen (NH 4-N) and percentage of dry matter (% DM) play an important role in ammonia volatilization during manure application to soils. Generally, liquid manure and slurry have a high rate of ammonia loss compared to solid manure. The dry matter content has been shown to significantly affect

ammonia volatilization. Reducing the dry matter content of dairy manure by dilution or separation has been shown to reduce ammonia emissions following land application. 2. Environmental factors: Temperature: Solar radiation increases the temperature of the manure. As manure temperature increases, ammonia volatilization increases, especially within the first few hours after manure is applied to the soil (50%). Researchers have found that 50 per cent of total nitrogen is volatilized as ammonia at a temperature of 30C compared to 35 per cent when the temperature is 25C. Manure applications should not be made when temperatures are high. Wind: An increase in wind speed will increase the rate of ammonia volatilization as the higher wind increases the mass transfer and air exchange between the manured surface and the atmosphere. Manure should be applied when the wind speed is low, and the weather is stable. Rainfall: Rainfall directly after manure application decreases the volatilization of ammonia because the rain improves infiltration of the ammonia into the soil and also reduces its evaporation. Generally, ammonia emissions decrease with an increase in relative humidity. 3. Manure application method and timing: The manure application method greatly affects ammonia losses, with the largest losses occurring from surface-applied manure that is not incorporated into the soil. Minimal losses occur if the nitrogen source is immediately incorporated into the soil. Incorporation of manure into soil is one of the most cost-effective measures for decreasing ammonia loss. Furthermore, applying liquid manure by band spreader or injection proved to be more cost-effective than measures designed to reduce ammonia emissions from buildings. 4. Soil characteristics and conditions: Soil conditions including the moisture content, texture, cation exchange capacity, pH and plant or residue cover all affect the rate and amount of ammonia loss. More ammonia emissions from peat and heavy clay soils than from sand and clay soil when liquid manure was applied to grassland. Ammonia volatilization is favored by calcareous (chalky) soils. These losses may be reduced by soil acidification through the use of soil amendment.

Prevent Ammonia Volatilization:

Land application measures to reduce ammonia emissions aim to minimize the amount of manure and time of exposure on the ground. A range of techniques (discussed below) are available for reducing ammonia emission during the land application of manure. Application method or incorporation method and external factors need to be taken into account when predicting ammonia volatilization following manure application. Ammonia volatilization is increased by higher temperatures and by increased wind speeds. Soil factors such as residue cover, soil pH and soil texture (sands vs. silt loams) can

affect ammonia loss but soil factors are usually secondary to the factors such as application method and manure type. The following are the currently available best management practices for reducing ammonia volatilization during the land application of manure. 1. Direct injection of manure into the soil reduces ammonia losses compared to surface application methods. The reduction in ammonia emissions by injection could reach up to 100 percent, but it will also result in the increase of nitrous oxide emissions from agricultural soils by up to 100 per cent. 2. Banding conserves ammonia by reducing the exposure of manure to the air, but the method works best under a crop canopy. The crop canopy both reduces advection (transfer of heat by horizontal flow of air), thereby inhibiting ammonia volatilization, and directly absorbs up to 40 per cent of any released ammonia. 3. The timing of application is an important consideration affecting the release of manure nitrogen into the atmosphere. Ammonia loss is generally greater during the spring and summer. Also, incorporation time and weather affect ammonia losses. 4. Some products can effectively reduce ammonia losses through either a binding or a pH effect. Dropping the manure pH below 7 before it is applied can reduce ammonia emissions. Urease inhibitors may also prove effective.

Impacts of Ammonia on Water

Water reacts with ammonia to form ammonium and hydroxide ions. Ammonia is often referred to as unionized ammonia. Ammonia is toxic to aquatic organisms but ammonium is non-toxic. There exists equilibrium in water between the toxic ammonia and the non-toxic ammonium. The equation shifts back and forth depending upon existing or introduced environmental changes. NH3 (aq) + H2O (l) (Ammonia in water) NH3 H2O (aq) (Ammonia+water) NH4 + (aq) + OH - (aq) (Ammonium + hydroxide ions)

The dynamic equilibrium between NH3 and NH4 + is affected by water temperature and pH (acidity). If ammonia is directly spilled into surface water or if water used by a fire department to depress an ammonia vapor cloud is allowed to reach surface water, aquatic life can be harmed. Even at a concentration of 0.02 mg/L (48 hour LC50) unionized ammonia is lethal to some sensitive freshwater fish. That equates to about a cup of unionized ammonia in one million gallons of water.

Eutrophication:
Eutrophication is a result of nutrient pollution (from deposition or run-off) into natural waters (creeks, rivers, ponds, or lakes). Eutrophication generally promotes excessive plant growth and decay, favors certain weedy species over others, and is likely to cause severe

reductions in water quality. In aquatic environments, enhanced growth of choking aquatic vegetation or algal blooms disrupt normal functioning of the ecosystem, causing problems such as a lack of oxygen in the water, needed for fish and other aquatic life to survive. The water then becomes cloudy, colored a shade of green, yellow, brown, or red.

Soil Acidification:
When ammonia reaches the soil surface, it usually reacts with water in the soil and is converted into its ionic form, ammonium (NH4+) and absorbes to the soil. The ammonium in the soil eventually disassociates or is nitrified into nitrite (NO2-) or nitrate (NO3-) by nitrifying bacteria, releasing H+ ions into the soil. If not taken up by biomass and converted to methane, the surplus H+ ions eventually lead to the formation of an acidic soil environment. The nitrogen left over in the soil will either be taken up by plants, stored in the soil, returned to the atmosphere, or will be removed from the soil in runoff or leaching. Even at extremely low concentrations aquatic life will be harmed by ammonia: Ammonia occurs naturally in the environment. A small amount of ammonia is generated when lightning strikes and reaches earth in rainfall. But most ammonia is produced by bacteria in water and soil as an end product of plant and animal waste decomposition. It is found in relatively low nontoxic concentrations in soil, air, and water and provides a source of nitrogen for plants. In soils and water ammonia will go through many complex biochemical transformations. These transformations constitute what is commonly known as the nitrogen cycle. For a more indepth discussion of the nitrogen cycle see related links. The danger ammonia poses for fish depends on the waters temperature and pH, along with the dissolved oxygen and carbon dioxide levels. Remember, the higher the pH and the warmer the temperature, the more toxic the ammonia. Also, ammonia is much more toxic to fish and aquatic life when water contains very little dissolved oxygen and carbon dioxide.

Impacts of Ammonia on air

After a release of ammonia the vapors will dissipate reacting with the moisture in the air to form ammonium and eventually return to earth in rainfall. Ammonium then quickly binds to the negatively charged soil organic matter and soil clays. Ammonium rarely accumulates in soil because bacteria will rapidly convert the ammonium that is not taken up by plant roots into nitrates (nitrification). Nitrates can also be absorbed by roots or may leach through the soil profile. Since ammonium is soil bound, unless the soil is washed away by rainfall events the contamination will likely stay put horizontally but leach vertically as nitrates through the root zone.

If the fire department suppresses an ammonia vapor cloud with water for a prolonged period of time the applied water may contaminate soil. In this instance the soil may require some method of remediation to prevent adverse environmental affects. When in gaseous form, ammonia has a short atmospheric lifetime of about 24 hours and usually deposits near its source. In particulate form ammonia can travel much further impacting a larger area. Both gaseous and particulate ammonia contribute to eutrophication of surface waters, soil acidification, fertilization of vegetation, changes in ecosystems,and smog and decreased visibility in cities and pristine areas. Since ammonia is one of the only basic species in the atmosphere, it readily reacts with strong acidic species in the atmosphere such as nitric and sulfuric acids, which are byproducts of combustion process including vehicle and industrial sources, to form ammonium salts, also known as fine particulate matter or PM2.5. Due to their small diameter (less than 2.5 microns (m)) and increased atmospheric lifetime of 15 days, these particulates are able to travel long distances before being dry or wet deposited to the ground surface. This allows them to travel from rural areas to urban locations where they mix and build up in the atmosphere leading to smog or transportation to other areas. Smog and Decreased Visibility: When ammonia combines with NOx and SOx emissions from industrial and vehicle combustion processes it forms fine particulates. These fine particulates are a contributor to haze/smog in cites and decreased visibility (haze) in pristine areas. Smog is also a human health issue leading to an increased rate of respiratory and heart diseases.

Health Impacts of Ammonia:

How does ammonia act in the body? When ammonia enters the body as a result of breathing, swallowing or skin contact, it reacts with water to produce ammonium hydroxide. This chemical is very corrosive and damages cells in the body on contact. Ammonia effects human and animal health both as a gas and as a particulate. The particulate form of ammonia has broader implications for the general public, where as the gaseous form is a localized concern for the health of animals and agricultural workers. What are the specific signs and symptoms of ammonia poisoning? Ammonia is corrosive. The severity of health effects depends on the route of exposure, the dose and the duration of exposure. Exposure to high concentrations of ammonia in air causes immediate burning of the eyes, nose, throat and respiratory tract and can result in blindness, lung damage or death. Inhalation of lower concentrations can cause coughing, and nose and throat irritation.