Manure Management Technology

Development Team
East National Technology Support Center

Manure Chemistry – Nitrogen, Phosphorus, & Carbon

August 2007 Manure Management Information Sheet Number 7

INTRODUCTION and moves rapidly in runoff and in soil solutions.

Buildup of nitrate in groundwater is a health
It’s hard to talk about manure management without concern; the concentration limit in drinking water is
referring to the complex chemistry involved. It’s 10 mg per liter. While in surface waters the
also hard to remember all that stuff we learned so concentration is rarely that high, nitrogen still
long ago--- especially when somebody starts contributes to eutrophication (excess plant growth).
throwing around words like ‘anoxic,’ Excessive use of nitrogen fertilizers is implicated in
‘mineralization,’ and ‘redox.’ This document is the expansion of a hypoxic area or “Dead Zone” in
intended to provide a compact overview of what the Gulf of Mexico.
happens to three critical elements—nitrogen,
The ammonia form of nitrogen can be an air quality
phosphorus, and carbon—during manure storage
concern. Manure nitrogen is often converted into
and treatment.
the ammonium (soluble) form by bacteria. If the
NITROGEN pH is above neutral, the manure is warm, and there
is nothing to work against ammonification, the
The element nitrogen (N) has many oxidation states ammonium changes into the ammonia (gaseous)
and can form numerous compounds. Elemental N2, form and volatilizes into the atmosphere. Ammonia
or diatomic nitrogen, composes 78% of the air we in significant concentrations is harmful to livestock
breathe, and nitrogenous compounds are and agricultural workers; it is also a precursor to
components of all living tissue. In manure, N harmful particulates and facilitates the formation of
occurs as nearly all of these forms at one time or undesirable gases.
another:
There are five natural processes that transform N
Nitrogen Formula Oxidation from one form to another: Fixation,
Species State
ammonification, synthesis, nitrification, and
Organic nitrogen Org-N denitrification.
Ammonia, NH3 -3
Ammonium ion NH4+ -3 • Fixation: the conversion of nitrogen gas [N2]
from the atmosphere into any form of nitrogen
Hydrazine N2H4 -2 used by plants and animals. The most familiar
Hydroxylamine NH2OH -1 example is the work done by Rhizobia bacteria
Nitrogen gas N2 0 attached to the roots of legumes, which can
reduce N2 from the atmosphere into NH3. A
Nitrous oxide N2O +1 certain amount of N2 is also transformed into
NO3 by lightening and delivered to the soil in
Nitric oxide NO +2 rain. Plants utilize N as either ammonium (from
Nitrous acid bacteria) or nitrate (from bacteria, lightening, or
HNO2 +3 fertilizer). Animals get their N by eating plants
Nitrite ion NO2- +3 or other animals.
Nitrogen dioxide NO2 +4
• Ammonification: the degradation of organic-N to
Nitric acid HNO3 +5 ammonium, usually by bacteria. This can
Nitrate ion NO3- +5 happen under both aerobic and anaerobic
conditions if the appropriate bacteria are
present.
Nitrogen is of concern to agriculture both as an
essential plant nutrient for building proteins and • Nitrification: converting ammonium to nitrite and
amino acids and as a potential water pollutant. then nitrate, in a type of biological oxidation.
The two bacterial species Nitrobacter and
Nitrogen, as nitrate or ammonium, is highly soluble
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 Nitrosomonas are most commonly associated to NO3 is interrupted or slowed by lack of
with this transformation. oxygen, the intermediate NH3 will be driven off.
• Synthesis: the biochemical mechanism that • Anaerobic digestion: Passing through a digester
converts ammonium or nitrate into living cells, has little effect on the total nitrogen content of
either plant cells or bacterial cells. (Animals manure. A negligible amount of N may be
cannot eat straight ammonium or nitrate and emitted as NH3, but the majority will be found
convert it.) as organic N and NH4 in solution in the digester
sludge. The ammonium content of digester
• Denitrification: The completion of the nitrogen sludge will be higher than that of raw manure.
cycle by returning N to the atmosphere as N2 Although the anaerobic conditions should favor
gas. Denitrifying bacteria convert NO3 to N2 production of ammonia, the ammonium is held
under anoxic (low oxygen) conditions. This can in solution by the pressurization of the vessel,
occur in soils that undergo periods of and the slightly acidic pH favorable to
saturation, either naturally or under cultivation methanogenic bacteria.
as in rice production.
• Gasification: a portion of the N in manure will be
After manure is excreted, the organic nitrogen, gasified into either N2 or N2O. This process is
ammonium, and urea in the feces and urine are still poorly understood and may be highly
subjected to treatment and storage. Urea is quickly variable depending on conditions. The ash and
converted to ammonium. Here are some of the char remaining after gasification is usually low
transformations that might occur, depending on in nitrogen.
how the manure is handled: • Pyrolysis: Some N will be found in the oil
• Storage: What happens to nitrogen in structures products, where it is considered a contaminant.
designed to store, rather than treat, manure The remaining N is usually found in solution in
depends on whether conditions are aerobic the watery waste remaining after the oils have
(plenty of oxygen) or anaerobic (no free been distilled off.
oxygen.) In aerobic conditions, the N will
• Composting: A portion of the N in the compost
largely remain in the manure as organic N or
pile is volatilized as NH3, and a small amount
ammonium. Aerobic conditions may exist in dry
may be emitted as N2O. The remainder is
stack storage, poultry litter storage, or systems
found either in the bodies of microorganisms as
specifically designed to aerate the manure. In
organic N, or as NO3, which is available to
anaerobic conditions, which usually apply, a
plants.
portion of N will probably be lost to the
atmosphere as NH3. • Land application: Raw (untreated) manure
applied to land contains nitrogen in the form of
• Anaerobic lagoons: Structures specifically
organic compounds and ammonium. Dryer
designed as anaerobic lagoons are not just for
manure from feedlots and poultry litter will also
storage. In a properly operating lagoon,
contain some nitrate-N. The organic nitrogen in
conditions foster anaerobic decomposition. pH
manure is broken down into forms plants can
will be at or above neutral, in contrast to
absorb over time. Nitrate is highly mobile in soil
storage facilities which are more acidic.
solution, as is ammonium to a lesser degree.
Manure has a long residence time in most
Both are readily used by crop plants.
anaerobic lagoons, allowing for complex
Unfortunately, they are also mobile in surface
chemical and biological interactions. Nitrogen
runoff, and may cause water pollution if not
will be converted into NH4 and NH3 by biological
properly managed. Manure management
activity. When conditions favor ammonia
calculations generally assume that most
volatilization, NH3 will be lost to the
available nitrogen in manure will be utilized by
atmosphere. Ammonification is accelerated by
plants or denitrified by soil microorganisms in
high pH and warmth.
three years. When land applied, manure can
• Aerobic lagoons: Under aerobic conditions, also lose nitrogen as ammonia through
where oxygen is freely available, far less volatilization. This occurs during application and
ammonia is generated than in anaerobic as the manure sits on the soil surface.
conditions. In these situations, N will be Incorporation or injection reduces these losses,
retained in solution as NO3 and NH4, and in the because the ammonium will be nitrified by soil
bodies of aerobic microorganisms as organic N. bacteria. In wet soils and under appropriate
Nitrogen converted to ammonium will be conditions, anaerobic bacteria may then
mineralized as NO3. If the conversion from NH4 denitrify the nitrate and give off nitrogen gas.

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PHOSPHORUS Under acidic anaerobic conditions, P can form the
gas phosphine (PH3). However, rather than
Phosphorus is a non-metal found in the same volatilizing like ammonia, phosphine usually
chemical family as nitrogen. The most common recombines with other constituents of the manure
oxidation states found in nature are +3, +5, and -3. and is not lost.
Phosphorus generally forms compounds with
oxygen, hydrogen, and halides [e.g. fluoride]. In Note that in treatments that reduce the mass of the
agriculture, we’re most familiar with it in fertilizer manure, like composting, gasification, pyrolysis,
compounds such as mono- and di-ammonium and digestion, the concentration of P increases
phosphate, triple super-phosphate, and as the because it does not go away.
plant-available ion in soils, orthophosphate (H2PO4- • Storage: When manure is stored as a solid, not
). Regardless of the actual chemical form of the much happens to the phosphorus; it will still be
phosphorus, the analyses of phosphorus fertilizers present as it was when stored. When stored as
are given as phosphate (P2O5). a liquid, the P tends to accumulate in the sludge
at the bottom of the storage unit, as organic P
Phosphorus (P) is an essential nutrient for both present in the bodies of microorganisms.
plants and animals. All DNA molecules contain
phosphorus. Plants need it for flowering and • Anaerobic digestion: Digestion has little effect
on P, other than moving some of the dissolved
reproduction, as well as energy exchange. Animals
portion into the bodies of bacteria that carry out
need phosphorus for a number of processes the anaerobic digestion process. All of the P
including energy processes, formation of bone, and present in the manure will still be present in the
building eggshells. digester sludge.
In manure, P is present in organic matter and as • Gasification: Since P is not a component of any
dissolved reactive phosphorus—DRP or of the gases produced in this process, all the P
orthophosphate. The dissolved form is easily present in the manure at the beginning of the
transported from crop fields to surface water in process will still be there at the end, contained
runoff, where it can cause nutrient imbalances in the ash and char residuals.
leading to eutrophication and other water quality • Pyrolysis: As with gasification, all of the P will
problems. end up in char and other residuals.
Because P does not easily form gases, it stays in the • Composting: At the end of the composting
manure through storage and treatment. Organic process, most of the P will be in organic form,
phosphorus is contained in the bodies of contained in live or dead microorganism bodies.
microorganisms in the manure. Dissolved reactive All of the initial P will still be present.
P in solution can be coagulated with metal • Land application: Ideally, all the P in land-
compounds and then aggregated into clumps that applied manure would be taken up by crop
will settle out by treating the manure with plants. In reality, some is transported in runoff,
flocculating polymers. Solids separation some moves into the soil profile, and some is
technology may partition up to 90% of P into the bound by metal ions (calcium, aluminum, and
solid portion of the manure if the separation process iron.) Soils have varied capacity for binding P,
is augmented with coagulants and flocculants. depending on pH, cation exchange capacity,
Solids separation without chemical assistance may rainfall, type of clay present, and presence of
metals (primarily aluminum and iron oxides.)
remove anywhere from a few percent of total P up Over time, all the easily available P in the root
to 60%, depending on how efficiently the method zone will be used by crops as long as the
separates out fine manure particles, where most of amount of manure applied is in balance with
the P is contained. crop needs. In many parts of the country,
excess manure has been applied for years and
Under certain conditions, (pH between 7 and 11 and
soils are heavily loaded with phosphorus that is
a sufficient amount of dissolved magnesium) P can slowly traveling down the soil profile, and may
combine with magnesium and ammonium to form never be fully utilized.
the crystalline compound struvite [magnesium
ammonium phosphate hexahydrate, CARBON
MgNH4PO4·6H2O]. Forced precipitation of struvite
has been investigated as a way of removing P from The abundant carbon atom is present in all forms of
manure effluent. terrestrial life. Carbon cycles through the soil,

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oceans, atmosphere, earth’s geology, and living produced in the interior of particles where there
things, entering into more chemical compounds is little oxygen. So much carbon is consumed
than any other element. that the mass may shrink by 50% or more.

Plants fix carbon from carbon dioxide (CO2) in the • Land application: The transformation of carbon-
atmosphere, converting most of it into sugars and containing compounds is similar to the
composting process but takes place more
starches. Animals eat the plants and convert the
slowly and without the increase in temperature.
carbon into animal tissue. The carbon in manure Organisms in the soil mineralize carbon in
comes from plant (and some animal) materials in manure into CO2, which is given off into the
livestock feed. A portion of the carbon consumed is atmosphere or retained in soil gasses. Some of
exhaled as methane (CH4), and of course, animals the carbon is bound into the soil as humic acid
breathe in oxygen and exhale CO2. (soil organic matter.) If the ratio of carbon to
nitrogen is high—for example, if the manure
A large amount of the organic matter in manure is contains a lot of sawdust or other bedding, or
actually the bodies of bacteria from the animal’s there is a large amount of residue on the soil
gut, along with some partly digested feed. Carbon surface— the available nitrogen in the soil may
is present in proteins, fatty acids, lipids, be immobilized by bacteria decomposing the
carbohydrates, cellulose, and lignins. carbonaceous material, leaving plants with less
nitrogen than they need for successful crop
During storage and treatment, much of the carbon production. High-carbon manures, including
in manure may be mineralized into CO2 or poultry litter and horse manure, benefit from
converted to CH4. composting before being land applied for this
reason.
• Storage: Biological activity continues in the
manure during storage. If the conditions are ADDITIONAL INFORMATION
aerobic, CO2 will be given off, and if anaerobic,
CH4 and smaller amounts of CO2 will be The fate of crop nutrients during digestion of swine
emitted. When manure is stored in anaerobic manure in psychrophilic anaerobic sequencing batch
lagoons, significant amounts of carbon are lost reactors. D.I. Massé, F. Croteaua and L. Massea,
as methane. Bioresource Technology Vol 98, Issue 15, November
2006
• Anaerobic digestion: Simple sugars, volatile
fatty acids, and alcohols degrade quickly – The Fate of Nutrients and Pathogens During Anaerobic
within hours–and are converted into CH4 and Digestion of Dairy Manure. Patrick Topper, Robert
CO2 with traces of hydrogen sulfide [H2S] and Graves, Thomas Richard, Penn State Agricultural and
water vapor. If the residence time is long Biological Engineering Cooperative Extension
enough, hemicellulose, fat, and protein will Publication G-71 June 2006
degrade in a few days. Cellulose and lignin are
Livestock and Poultry Environmental Stewardship
usually left intact. The gasses given off by the
(LPES) Curriculum, Lesson 25, Manure Treatment
digester will contain 40% to 70% methane.
Options. [All of the LPES series are worth studying.]
• Gasification: Under low-oxygen conditions and Can be downloaded at
high temperatures, carbon compounds are http://www.lpes.org/les_plans.html
converted into combustible gasses, leaving
Evaluation of On-Farm Composting of Turkey Brooder
behind mineral ash. The gasses contain CO,
Litter. John Chastain, P. Andrew Rollins, Kathy Moore,
CO2, CH4, C2H4, N2, and H2.
ASAE Paper # 054064, July 2005
• Pyrolysis: Manure is converted under high The U.S. Department of Agriculture (USDA) prohibits discrimination
temperatures, pressure, and absence of oxygen in all its programs and activities on the basis of race, color, national
into oil, char, and waste gasses. Carbon origin, age, disability, and where applicable, sex, marital status, familial
monoxide (CO) is actually pumped into the status, parental status, religion, sexual orientation, genetic information,
political beliefs, reprisal, or because all or a part of an individual’s
process to scavenge free oxygen, and the income is derived from any public assistance program. (Not all
carbon in the manure is transformed into prohibited bases apply to all programs.) Persons with disabilities who
burnable hydrocarbons similar to light crude oil. require alternative means for communication of program information
This process is a variant of the methods used to (Braille, large print, audiotape, etc.) should contact USDA’s TARGET
Center at (202) 720–2600 (voice and TDD). To file a complaint of
make charcoal from wood. discrimination, write to USDA, Director, Office of Civil Rights, 1400
Independence Avenue, SW., Washington, DC 20250–9410, or call
• Composting: Carbon-containing compounds are (800) 795–3272 (voice) or (202) 720–6382 (TDD). USDA is an equal
attacked by bacteria, actinomycetes, and fungi opportunity provider and employer.
under aerobic conditions, and the carbon is
primarily mineralized into CO2. Some CH4 is
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