This is a very quickly assembled set of slides that I discussed with my nutrient management class on 4/19/2013

2. The remains of a fertilizer plant burn after an explosion in
West, TX (near Waco) Photograph: Mike Stone/Reuters

3. A relatively small fertilizer retail and storage facility – NOT a manufacturing facility

4. Close proximity to a surprising # of institutional facilities

5. More than 150 people were treated for injuries at the local
hospital as well as at Waco, 18 miles away, and Dallas, 80 miles
away.
Units from 30 fire departments brought the blaze at the West
Fertilizer Company plant under control by midnight.
Fears that a second fertiliser tank might explode receded but
authorities continued to evacuate residents amid concern about
toxic fumes.
David Argueta, vice-president of operations at Waco's Hillcrest
Baptist medical centre, said staff had treated lacerations and
orthopaedic-type injuries. "We are being told that we have seen
most of the patients, and it's now turned into a search-and-
rescue operation on scene."

7. Texas City Disaster 1947

8. On April 16, 1947 – 66 years and one day to yesterday’s explosion – the
Grandcamp was being loaded with ammonium nitrate as well as tobacco and
government-owned ammunition. Cigarette smoking, although officially
banned, was a common practice by longshoremen on the docks. Just two
days prior to the explosion, a cigarette had caused a fire on the docks. On the
morning of April 16, smoke was spotted deep within one of the Grandcamp’s
holds.
Some water and an extinguisher were used to fight the fire, but hoses were
not employed for fear of ruining the cargo; there were already 2,300 tons
loaded on the ship. While the ammunition was removed from the ship, the
crew attempted to restrict oxygen to the hold in hopes of putting out the fire.
Apparently they did not realize that because of ammonium nitrate’s chemical
composition, it does not require oxygen in order to burn.
By 9 a.m., flames had erupted from the hold and within minutes it exploded.
The blast was heard 150 miles away and was so powerful that the ship’s 1.5-
ton anchor was found two miles away. The force of the explosion lifted
another ship right out of the water. People working at the docks were killed
instantly.

9. Pieces of flaming debris damaged the oil refineries in the area. A
nearby Monsanto chemical storage facility also exploded, killing 234 of
the 574 workers there. Nearly all of the survivors were seriously injured.
A residential area of 500 homes was also leveled by the blast.
Another ship, the High Flyer, which was carrying similar cargo, was
pushed completely across the harbor. The crew fled when it came to
rest, failing to notice that a fire had started and the next day their ship
also exploded. Two people died.
In all, 581 people died and 3,500 were injured. The explosion caused
$100 million in damages. A long-disputed court case over the cause of
the blast was resolved when Congress granted compensation to 1,394
victims. They received a total of $17 million in 1955. The port was
rebuilt to handle oil products only.”

10. The Port Neal fertilizer plant explosion occurred on December 13, 1994 in the
ammonium nitrate plant at the Terra International, Inc., Port Neal Complex, 16 miles
south of Sioux City, IA. Four workers at the plant were killed by the explosion, and
eighteen others were injured. The seven-storey building at the seat of the blast was
completely destroyed, leaving only a crater, and significant damage was inflicted to the
surrounding structures. Four nearby electricity generating stations were disabled by the
explosion, and the effects of the blast were felt up to 30 miles away. A high-voltage line
running adjacent to the plant and over the Missouri River was damaged, disrupting
power in the neighboring state of Nebraska. Two 15,000-ton refrigerated ammonia
storage tanks were ruptured, releasing liquid ammonia and ammonia vapors which
forced the evacuation of 1,700 residents from the surrounding area.
An investigation conducted by the United States Environmental Protection Agency (EPA)
concluded in 1996 that the explosion was initiated by an accelerated thermal
decomposition reaction as "a direct result of unsafe operating procedures and
conditions" at the plant. The EPA had conducted a safety audit at the plant just eight
months prior to the explosion. The plant was Iowa's largest producer of nitrogen-based
fertilizers and its loss contributed to a national 50% increase in the cost of fertilizer by
the following year (NEED TO FACT CHECK).

11. SIOUX CITY, Iowa, Dec. 23 1997 /PRNewswire/ --
Terra Industries Inc. (NYSE: TRA) announced today that it
has reached a settlement with Industrial Risk Insurers (IRI)
on its insurance claims for property damages and business
interruption losses arising from the 1994 explosion at Terra's
Port Neal, Iowa fertilizer plant. IRI is one of the six insurance
carrier defendants Terra sued in April of this year in Sioux
City federal district court to recover on its claims. Under the
settlement, IRI agreed to pay Terra its proportionate share
(50 percent of the overall insurance coverage) of a total claim
fixed at $321 million. Previously, Terra settled with all of the
other five insurance carrier defendants, who collectively paid
the other 50 percent share of a $321 million settlement.

12. Inspections of the West Fertilizer Co. by various agencies
in recent years resulted in fines of more than $12,000 for
lax compliance in developing risk management and
security plans.
In 2006, the Environmental Protection Agency fined West
Fertilizer $2,300 after discovering the company had failed
to update its risk management plan, which includes an
analysis of the potential consequences of a worst-case
accident as well as its emergency planning information.
The following slides contain publicly accessible info that
needs fact checking but suggests that the West Fertilizer
company had a poor track record with respect to record
keeping and state and federal program compliance

13. The EPA requires such plans of all facilities that store large quantities of
ammonia. The company was supposed to update its plan in 2004, but didn’t do
so for another two years, inspectors found. Inspectors also found that the
company kept poor training records, had not developed a formal written
maintenance program, and had operating procedures that failed to address the
“consequences of deviation.”
According to the EPA, the company “certified they corrected the deficiencies,”
and filed and updated plan in 2011 as required.
Last summer, the company was fined $10,100 by the U.S. Pipeline and Hazardous
Materials Safety Administration after an inspector determined that it
transported anhydrous ammonia in non-specification unauthorized cargo tanks
and did so without the required security plan. Such a plan is aimed at thwarting
theft of a material that could be used to build an explosive.
West Fertilizer paid the government $5,250 after asking to pay a lower amount
because of problems with “finances,” according to agency documents.

14. In Texas, commercial fertilizer operations must register with the Office of the
State Chemist’s Feed and Fertilizer Control Service. The agency, part of Texas
A&M AgriLife Research, appears primarily to test quality of fertilizer content.
Recent records show West Fertilizer had nine samples tested in 2011, failing two.
State Chemist Tim Herrman also said the plant was inspected recently, but
declined to provide details.
The Texas Commission on Environmental Quality also collects air quality
complaints against businesses. Two have been filed against West, according to
state records. One, filed in 2002, was descriptive: “THERE IS A CLOUD OF DUST.
PARTICLES ARE FALLING LIKE SNOW AROUND TOWN. PEOPLE ARE AFRAID TO
COMPLAIN, HOWEVER THIS IS EFFECTING NEIGHBORS HEALTH WITH SCRATCHY
THROATS, COUGH AND SNEEZING.”
It’s unclear how this was resolved.
The second complaint, filed in 2006, was of a strong smell of ammonia coming
from the plant.

15. Fertilizer is regulated at both the federal
and state levels. Federal agencies of
jurisdiction include the Department of
Homeland Security, the Environmental
Protection Agency, the Occupational
Health and Safety Administration and the
Department of Transportation. At the state
level, fertilizers are regulated by state
departments of agriculture,
transportation, environmental protection…

16. Facilities storing anhydrous ammonia in quantities of 10,000 lbs.
or more are required to have an Environmental Protection Ag
ency (EPA) approved Clean Air Act Risk Management Program
plan to address accidental releases of ammonia. Each facility
covered under the act is required to conduct an offsite
consequence analysis for a worst case accident, a hazard
assessment and an accident prevention program.
Facilities storing ammonium nitrate in quantities of 400 lbs. or
more are regulated under the Department of Homeland Security.
Additionally, The National Fire Protection Association (NFPA)
code 490 sets standards for the storage of ammonium nitrate.
Ammonium nitrate is also regulated by the Department of
Transportation
.

17. According the American National Standards
Institute’s (ANSI) Standard for Storage and
Handling of Anhydrous Ammonia, ammonia is
extremely hard to ignite and is a relatively
stable compound. The conditions favorable
for ignition are seldom encountered during
normal operations due to the high ignition
temperature required.

19. Each purchaser and seller will be required to apply for an Ammonium Nitrate
(AN) Registered User Number with the Department, and each applicant will be
screened against the Terrorist Screening Database (TSDB). Following the
screening process, approved individuals will be issued an AN Registered User
Number, which will allow them to engage in the sale, purchase, or transfer of
ammonium nitrate.
Transactions involving the sale or transfer of ammonium nitrate will be
regulated at the point of sale and procedures for reporting a theft or loss of
ammonium nitrate will be established. Ammonium nitrate sellers will be
required to deny sale or transfer of ammonium nitrate to individuals who:
1) Do not possess a valid AN Registered User Number accompanied by a valid
photo ID; or
2) Are not authorized by a person possessing a valid AN Registered User
Number to act on their behalf as an agent.
The regulation will require businesses to keep records of all ammonium nitrate
transactions for two years, and DHS may inspect and audit facility records to
ensure compliance.

20. In 1991, there were 58 U. S.
ammonium nitrate plants
located in 22 states producing
about 9 million tons of
ammonium nitrate.
Approximately 15 to 20
percent of this amount was
used for explosives and the
balance for fertilizer.

21. Public comment by CF Industries representative (CF is the
largest US manufactor of fertilizer grade AN) on 4/4/2013:
“Even though it (AN) has always made up a small part of
total U.S. nitrogen fertilizer usage, over the last decade,
and especially over the last six years, the ammonium
nitrate market has contracted substantially. The principal
reason for this is that new security regulations governing
the handling of ammonium nitrate by distributors and
dealers have led many of them to decide not to carry it. In
those regions where ammonium nitrate is not strongly
preferred, many distributors and dealers have stopped
buying the product. Today, the U.S. market is down to
around a million short tons, almost half of what it was just
a few years ago.”

23. Ammonium nitrate

24. AN sold in the market
contains an average of 33.5
percent of nitrogen. This
compound is very soluble in
water; and if the water which
AN was dissolved at is heated,
the by- product will be nitrous
oxide which is commonly
referred to as laughing gas.

25. The processes involved in the production of ammonium
nitrate in industry, although chemically simple, are
technologically challenging. The acid-base reaction of
ammonia with nitric acid gives a solution of ammonium
nitrate: HNO3(aq) + NH3(l) → NH4NO3(aq)
For industrial production, 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% to
99.9% concentration (AN melt), depending on grade.
The AN melt is then made into "prills" or 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.

26. When a person has inhaled AN, move him or her out to an open area so that fresh air
can be inhaled. In case of large dose inhalation, professional medical help must be
called immediately. While waiting for the help to arrive, it is important to take the
victim away from the site and transfer him or her to an open area where the air is
clean. If the patient is not breathing, CPR and mouth to mouth resuscitation must be
performed as soon as possible. Once the ambulance has arrived, oxygen will be
administered to facilitate the respiration.
For eye contact, the affected eye must be flushed with running water for at least
fifteen minutes.
When ammonium nitrate comes into contact with the skin, flush the area with
running water for at least fifteen minutes as well. You can wash it with soap, and then
an emollient can be used to cover the irritated area. It is very important to get the
soiled clothing away from the body and they should be washed thoroughly before
allowing the person to wear them again. The ammonium nitrate MSDS is very clear
that in any of these conditions, seeking medical attention is always part of the
protocol and should not be missed.
Derived from the Ammonium Nitrate MSDS

27. If someone has ingested AN, call medical help
immediately. As stated in the ammonium
nitrate MSDS, you should not induce vomiting.
Always wait for the medical team to arrive and
always tell them how much has been ingested
and what time the incident had happened. If
the patient is unconscious and unresponsive,
do not give anything by mouth.
Ammonium nitrate has an LD50 of
2217 mg/kg,which for comparison is about
two-thirds that of table salt.

28. The dissolution of AN in water is an endothermic reaction. There are two main
reactions that occur. When the polar molecules of the water separate the nitrate
ion from the ammonium ion, this produces an endothermic reaction. Heat is
being absorbed so the person may feel cold. But when the ions that have been
separated are now suspended in the remaining water in the solution, they
become hydrated and this process is an exothermic reaction. An exothermic
reaction produces heat since it gives off energy. More energy is required to
separate the ammonium and nitrate ions than to hydrate the ions, so the only
reaction that is physically felt is the endothermic one.
AN is used in instant cold packs

29. There are two major classes of incidents involving AN that
result in explosions:
1) explosion happens by the mechanism of shock-to-detonation
transition. The initiation happens by an explosive charge going off in the
mass, by the detonation of a shell thrown into the mass, or by
detonation of an explosive mixture in contact with the mass.
2) explosion results from a fire that spreads into the ammonium nitrate
itself or from a mixture of ammonium nitrate with a combustible
material during the fire. The fire must be confined at least to a degree
for successful transition from a fire to an explosion (a phenomenon
known as "deflagration-to-detonation transition", or DDT). Pure,
compact AN is stable and very difficult to ignite, and there are numerous
cases when even impure AN did not explode in a fire.

30. ANFO (or AN/FO, for ammonium nitrate/fuel oil) is a widely used
bulk industrial explosive mixture.
It consists of 94 percent porous prilled ammonium nitrate (NH4NO3),
(AN) that acts as the oxidizing agent and absorbent for the fuel – six
percent number 2 fuel oil (FO).
ANFO has found wide use in coal mining, quarrying, metal mining,
and civil construction in undemanding applications where the
advantages of ANFO's low cost and ease of use matter more than the
benefits offered by conventional industrial explosives, such as water
resistance, oxygen balance, high detonation velocity, and
performance in small diameters.
It accounts for an estimated 80% of the 6,000,000,000 pounds of
explosives used annually in North America.

31. ANFO under most conditions is cap-
insensitive, and so it is classified as a
blasting agent and not a high explosive.
It reacts through detonation rather than
deflagration with a velocity of about 3,200
meters per second.
It is a tertiary explosive consisting of distinct
fuel and oxidizer phases and requires
confinement for efficient detonation.

32. AN prills used for
explosive applications are
physically different from
fertilizer prills; the prills
used for explosive
application contain
approximately 20% air.
These prills are generally
called explosives grade,
low density, or industrial
grade ammonium
nitrate. Charging a hole with ANFO for rock blasting

33. The ANFO car bomb was adopted by the IRA in 1972
and, by 1973, IRA operatives were using > 20 tons of
AN/yr.
ANFO was also routinely used by groups such as the
Revolutionary Armed Forces of Colombia (FARC), and
Basque separatists (ETA).
Ramzi Yousef used ANFO to try to destroy the World
Trade Center in 1993.
A more sophisticated variant of ANFO (ammonium
nitrate with nitromethane as the fuel called ANNM) was
used in the 1995 Oklahoma City bombing.

34. The popularity of ANFO is largely
attributable to its low cost and high
stability. In most jurisdictions,
ammonium nitrate need not be
classified as an explosive for transport
purposes; it is merely an oxidizer. Many
mines prepare ANFO on-site using the
same diesel fuel that powers their
vehicles.

36. Ammonium nitrate (AN) – produced by reacting nitric acid, an intermediate chemical
feedstock produced from ammonia, with ammonia to form a concentrated, watery
solution that is subsequently solidified in a prilling or granulation process. Ammonium
nitrate is a solid fertilizer (containing approximately 34 percent nitrogen) typically
applied in solid form. Ammonium nitrate is water soluble and used in various fertilizer
solutions.
Calcium ammonium nitrate (CAN) – a mixture of AN and calcium or magnesium
carbonate (containing 25-28 percent nitrogen), produced by mixing calcium and/or
magnesium carbonate into an ammonium nitrate solution before the solidification
process. The lime content of CAN also helps to neutralize soil acidity.
Calcium nitrate (CN) – produced by dissolving a calcium salt such as limestone or the
calcium phosphate of phosphate rock in nitric acid. In the latter case, it is a co-product
with nitrophosphate products. CN is used to remedy plant deficiencies in calcium and
ameliorate soil acidification. It contains 15.5 percent nitrogen in nitrate form and 19
percent water-soluble calcium. The product is water soluble and particularly suited for
water-born fertilizer application systems.
Potassium nitrate (PN) – produced by reacting sodium nitrate with potassium chloride.
Potassium nitrate is used as a potassium and nitrogen fertilizer. Potassium nitrate
contains 13.5 percent nitrogen and 45 percent water-soluble potassium as K2O. The
water suitability makes it particularly suited for liquid-based applications.
NITRATE FERTILIZERS

38. AN vs. Urea – understanding their participation in the N cycle

41. More data from YARA funded studies

42. CAN (and AN), due to a higher bulk density and lower nitrogen concentration,
has more homogeneous spreading characteristics than urea. Wind degrade
spreading homogeneity with urea more than with AN/CAN, resulting in
significant local over- or under supply.

44. What is this blue thing on the top of the tractor?