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1、AMMONIUM NITRATE EXPLOSIONS:LESSONS LEARNED Ammonium nitrate(AN)is a chemical compound with the power to feed billions but also the potential to devastate.AN is the most potent,economical,and convenient fertilizer on the market;thus,AN continues to be stored in large quantities in ports and other pl
2、aces around the world.However,the recent catastrophic explosion in Beirut is a reminder of the hazards associated with the improper storage and use of AN,as well as the need for diligent enforcement of its regulations.Unless everyone working with ANmanufacturers,sellers,users,first responders,and re
3、gulatorsis more aware of the hazards of AN and diligently implements safety rules,then future accidents with AN will be inevitable.2 Copyright 2021 American Chemical Society.All rights reserved3TABLE OF CONTENTSChapter 1.Major explosive accidents involving ammonium nitrate.1.1 The Beirut disaster:ex
4、plosion of a significant quantity of ammonium nitrate.1.2 Historical review of ammonium nitrate explosive accidents.Figure 1.Accidents of ammonium nitrate around the globe.Figure 2.Distribution of AN accidents that happened during storage,transportation,or manufacturing/processing.Chapter 2.Ammonium
5、 nitrate synthesis,formulations,and related patents.2.1 How ammonium nitrate is made.Can it be made more stable?.2.2 Preventing misuse of ammonium nitrate-based fertilizers.Table 1.Safer ammonium nitrate formulations.2.3 Patents related to ammonium nitrate as fertilizers.Figure 3.Number of patent pu
6、blications yearly on ammonium nitrate fertilizers from the top four countries.Chapter 3.The explosive nature of ammonium nitrate.3.1 Proposed mechanisms of ammonium nitrate decomposition and explosion.3.2 Why ammonium nitrate explodes.Chapter 4.Hazards during the recovery phaseafter ammonium nitrate
7、 explosions.4.1 Pollutant gases.4.2 Carcinogens such as polycyclic aromatic hydrocarbons,silica and asbestos.Figure 4.Number of published articles per year related to the hazards of polycyclic aromatic hydrocarbons,silica,or asbestos,according to the CAS content collection.Chapter 5.Regulations on a
8、mmonium nitrate storage and transportation.5.1 Why large amounts of ammonium nitrate are stored.Figure 5.The top six countries in ammonium nitrate production.Figure 6.Worldwide import amount of ammonium nitrate from 2002 to 2018 and top six countries in ammonium nitrate import or export.5.2 Regulati
9、ons and rules for ammonium nitrate.Table 2.Regulations and guidelines for storage and handling of ammonium nitrate.Figure 7.Timeline for ammonium nitrate-related accidents and regulations in the United States.Table 3.Regulations/guidance about ammonium nitrate in the United States.Figure 8:Ammonium
10、nitrate safe storage guidelines.5.3 Alternative nitrogen fertilizers.Table 4.Comparison of ammonium nitrate with alternative nitrogenous fertilizers.Table 5.fertilizer mixtures containing nitrogen.Chapter 6.Summary and perspectives.Appendix 1:List of ammonium nitrate disasters.References.Research wo
11、rking team.5 5 6 6 7 7 7 8 10 11 11 12 12 14 15 15 15 17 18 18 18 19 20 20 21 22 23 24 24 25 26 27-31 32-37 38 Copyright 2021 American Chemical Society.All rights reservedThe catastrophic explosion in Beirut was one of the worst accidents caused by ammonium nitrate(AN)in history.Since the explosion,
12、there has been a dramatic increase in interest concerning the safety aspects of AN.Herein,we review the history of accidents involving AN around the world,most of which happened during storage or transportation,showing a general lack of awareness of safe handling and storage of AN.We then discuss sa
13、fer formulations of AN and strategies for preventing accidents and misuse found in the patent literature.The explosive nature of AN is then evaluated.In addition,we review potential environmental and health consequences of toxic gases and chemicals released during the AN explosion.We then explore th
14、e regulations from many countries and international agencies related to AN with important safety rules highlighted.This report serves as an introduction to the physical and chemical properties of AN,its hazards and safety rules,and provides a useful resource to scientists in the AN research field,as
15、 well as business leaders in the fertilizer and related chemical industries.EXECUTIVE SUMMARY NOTABLE HIGHLIGHTS:Since the beginning of the 20th century,there have been nearly 40 accidents involving AN,most in storage or transportation.The catastrophic explosion in Beirut was one of the worst accide
16、nts in history based on lives lost and property damaged caused by AN,comparable only to explosions of large amounts of AN in Texas City,United States (1947);Toulouse,France(2001);and Tianjin,China(2015).AN is made by reaction of ammonia with nitric acid in water followed by careful evaporation of th
17、e water.Additives for AN have been used to control its form and reduce the hazards of its storage and handling.Strategies for preventing misuse of AN-based fertilizers found in recent patent literature are provided.AN is an explosive hazard,as it is both a fuel and an oxidizer.It decomposes into gas
18、es which are more stable than AN and take up much more volume;the reaction also generates large amounts of heat.AN explosions generate large amounts of toxic gases and carcinogens.Safe storage of AN requires ventilation,isolation from combustible materials,temperature control,control of the amount i
19、n storage,fire protection,and avoidance of combustible contaminants.SINCE 1901,THERE HAVE BEEN NEARLY 40 ACCIDENTS INVOLVING AMMONIUM NITRATE4 Copyright 2021 American Chemical Society.All rights reserved5CHAPTER 1.MAJOR EXPLOSIVE ACCIDENTS INVOLVING AMMONIUM NITRATE METRIC TONS OF AMMONIUM NITRATE C
20、AUSED THE BEIRUT EXPLOSION2,750by an explosion that sent up a cloud of smoke and flashes of light from the stored fireworks.Half a minute later,a second,stronger explosion rocked central Beirut,sending a reddish-brown cloud surrounded by a white condensation cloud into the air.The reddish-brown colo
21、r of the smoke was caused by nitrogen dioxide(NO2),a byproduct of AN decomposition,present in a mixture with other nitrogen oxides(NOX).The white cloud was likely water vapor forced into the air by the shock wave of the explosion.3 By studying the blasts effect on nearby buildings,video of the Beiru
22、t accident shows that in the eighth of a second after the explosion occurred,its spherical shockwave grew to roughly 240 meters in diameter.It was estimated that the blast was roughly equivalent to that of several hundred tons of TNT.4 For comparison,the atomic bomb dropped on Hiroshima,Japan,in 194
23、5 had a yield of at least 13,000 tons of TNT and damaged and destroyed buildings within 1.5 miles of the site of the explosion.4,5The crisis created by the explosion,which included the destruction of 85%of the grain silos in Beirut,comes on top of an already crippled economy,the coronavirus pandemic
24、,and regional tensions.1.1 THE BEIRUT DISASTER:EXPLOSION OF A SIGNIFICANT QUANTITY OF AMMONIUM NITRATE.The catastrophic explosion in Beirut was one of the worst accidents caused by ammonium nitrate(AN)in history.On August 4,2020,a large amount of AN in a storage hangar at the Port of Beirut exploded
25、,causing nearly 300 deaths,6,000 injuries,and enormous property damage,leaving an estimated 300,000 people homeless.1,2Lebanese authorities confirmed that the explosion was caused by 2,750 tonnes(metric tons)of AN;it was detected by the United States Geological Survey as a seismic event of magnitude
26、 3.3,and is considered one of the most powerful non-nuclear explosions in history.2 The Beirut explosion was comparable to explosions of large amounts of AN in Texas City,United States(3,000 tonnes,1947);in Toulouse,France(200-300 tonnes,2001);and in Tianjin,China(800 tonnes,2015).On the afternoon o
27、f August 4,2020,a fire broke out in Warehouse 12,followed shortly thereafter Copyright 2021 American Chemical Society.All rights reserved61.2 HISTORICAL REVIEW OF AMMONIUM NITRATE EXPLOSIVE ACCIDENTS Since the beginning of the 20th century,there have been nearly 40 large accidents involving AN world
28、wide.Details of each of these accidents are shown in Figure 1 and Appendix 1.Eight of these accidents involved deaths of more than 100 people.In nearly all of these accidents,material damage was extensive.Most of these accidents occurred during the storage or transportation of AN.Indeed,17 accidents
29、 occurred in storage facilities alone due to unsafe operating procedures and conditions,such as storage with highly flammable materials.An additional 15 accidents took place during transportation,while a further 7 occurred while evaporating AN solutions during manufacturing or from attempts to break
30、 up aggregated AN with industrial explosives(Figure 2).It is also worth mentioning that among all the major accidents,about half of them occurred in the last 20 years during storage or transportation.Analysis of these incidents shows that AN explosions are almost always preceded by fires or other ig
31、nition sources.Figure 1.Accidents of ammonium nitrate around the globe.Major accidents are those that involved more than 1,000 tonnes of AN or caused more than 30 deaths during the explosion(Five of the minor accidents are not shown in the figure).Brooklyn,NY April 14,1920 1919 tonnesTexas City,TX A
32、pril 16,1947 2956 tonnesMAJOR INCIDENTS MINOR INCIDENTSFaversham,UK April 2,1916 700 tonnesBrest,France July 28,1947 1700-3309 tonnesToulouse,France Sept 21,2001 200-2300 tonnesLebanon,Beirut August 4,2020 2750 tonnesTessenderlo,Belgium April 29,1942 150 tonnesOppau,Germany Sept 21,1921 450 tonnesNe
33、yshabur,Iran February 18,2004 399 tonnesPort Tianjin,China August 12,2015 800 tonnesRyongchon,North Korea April 22,2004 Unknown tonnes Copyright 2021 American Chemical Society.All rights reserved7Figure 2:Distribution of AN accidents that happened during storage,transportation,or manufacturing/proce
34、ssing,shown as percentage with actual number in parenthesis.NUMBER OF ACCIDENTSManufacturing/processing 18%(7)Storage 44%(17)Transportation 38%(15)CHAPTER 2.AMMONIUM NITRATE SYNTHESIS,FORMULATIONS,AND RELATED PATENTS 2.1 HOW AMMONIUM NITRATE IS MADE.CAN IT BE MADE MORE STABLE?Ammonium nitrate(AN)is
35、made by reaction of ammonia with nitric acid in water followed by careful evaporation of the water:NH3+HNO3 NH4NO3 Ammonia is most often prepared by the Haber-Bosch process from atmospheric nitrogen,while nitric acid is prepared from the combustion of ammonia.6,7 This method uses starting materials
36、that are thus most commonly made together or near one another.The reaction gives off significant amounts of heat,so the AN is made in aqueous solution.The water must be removed to yield the solid AN,most often by evaporation.In the early 20th century,there were at least four instances of explosions
37、caused during the evaporation process.8 While AN is stable at the usual temperatures of its manufacture and purification,impurities may lower the stability of AN or provide fuel for combustion or explosion.At least one AN explosion was caused by the use of contaminated nitric acid in its production;
38、in another case,an explosion was triggered by air sprayed with oil from Copyright 2021 American Chemical Society.All rights reservedmachinery into cooling AN.Whats more,temperature variations within a facility can lead to AN mixtures being heated above their decomposition temperatures during evapora
39、tion,causing fires or explosions.AN can absorb water or change crystal forms,leading to undesirable masses(agglomerates)that are unusable.The most important change in crystal form of AN occurs at 32 C.This transition in crystal form is associated with a large volume change,which causes cracks in par
40、ticles,making them more susceptible to water absorption and agglomeration.7 For these reasons,temperature control is essential during the manufacture and storage of AN.To avoid the formation of agglomerates,AN is formed into prills or granules.Prills,resembling grains of rice,are formed by forcing m
41、olten AN through nozzles.Granules are formed by clumping smaller particles with binding agents.9 Additives have also been used to make AN safer to handle and store for use as a fertilizer with varying degrees of success.For example,potassium compounds have been used to increase the stability of AN t
42、o phase transition and sensitivity to explosion or detonation;nitrogen-potassium and nitrogen-phosphorus-potassium(NPK)fertilizers have improved stability.Potassium nitrate has been added to AN to increase its physical stability,but because of the added nitrate,the mixtures with AN are still strong
43、oxidants.Additionally,calcium and magnesium nitrate have been added to AN in small amounts to improve its physical stability,but the mixtures more easily absorb water from the atmosphere.Calcium ammonium nitrate(CAN),prepared from AN and calcium carbonate,is used in some cases as an alternative to A
44、N.In Finland,a commercial product(“FinnCAN”)was prepared from AN and the mineral phlogopite.7 FinnCAN contains 27%nitrogen(versus 34%nitrogen in CONTROL OF THE FORM OF AMMONIUM NITRATE IS IMPORTANT TO REDUCE ITS POTENTIAL HAZARDS8fertilizer-grade AN)and has improved stability to temperature changes
45、over unstabilized or ammonium sulfate-stabilized CAN.7 Aluminum sulfate has also been used as a drying additive for AN.Clays and inorganic compounds have been used as nucleating agents to improve the stability of AN granules or prills by reducing their size and thus the strains caused by temperature
46、 changes.Other additives have also been tried,such as surfactants,but some of them act as fuels for the AN,while others are either incompatible with the use of the stabilized AN as fertilizer or decrease its stability,increasing the risk of explosion or detonation.As a result,alternatives to AN have
47、 been tried,such as urea and ammonium sulfate;however,these alternatives are less suitable.For example,urea evaporates,leading to rapid nitrogen loss after application to fields.102.2 PREVENTING MISUSE OF AMMONIUM NITRATE-BASED FERTILIZERSAlthough the millions of tonnes of AN produced worldwide are
48、mainly used as fertilizer,AN is widely used in explosives for peaceful means.In fact,the second most common use is as a componentthe oxidizerof industrial explosives.The mixtures of AN with fuel oil(ANFO)and AN with nitromethane(ANNM)form powerful explosives that are commonly used in mining,Copyrigh
49、t 2021 American Chemical Society.All rights reservedquarrying,and construction.Unfortunately,as the components are relatively easy to obtain and inexpensive,ANFO and ANNM are also favorites of terrorists.AN therefore has the dubious distinction of being involved in not just the most deadly industria
50、l accidents as discussed in Section 1.2,but also in some of the most deadly terrorist attacks,such as the bombing of the Alfred P.Murrah Federal Building in Oklahoma City in 1995,which killed 168 people.Afghanistan banned the import and storage of AN in 2009 due to its use in improvised explosive de
51、vices(IEDs).In 2010,Afghanistan also banned CAN,a form of AN valued for its stability toward accidental explosion.However,AN or CAN are produced in large quantities and can still be easily smuggled for use in explosives.As a result,in 2012,60%of IEDs in Afghanistan were made with AN derived from the
52、 fertilizer CAN.11 IEDs were deployed often in Afghanistan(14,500 events in 2012)and there were approximately 6,000 IED events around that time annually outside of Afghanistan.12Consider CAN,which has been used for decades precisely because it is much less likely than AN to accidentally explode.CAN
53、is a mixture of AN and calcium carbonate,which comes from limestone or dolomite.The calcium component acts as a stabilizera diluentmaking a product in which an explosive reaction is difficult to sustain:it is not likely to explode by accident.13-16 Unfortunately,there are easy ways to convert CAN in
54、to something that can explode on command:separating the soluble AN from the insoluble calcium carbonate(the wet method)or grinding the CAN into a fine powder(the dry 89method).17-18 Therefore,it is not enough to make fertilizers that do not accidentally explode;it is also important to make ones that
55、 cannot be easily made to explode.A sampling of documents describing efforts to prevent accidental explosion or misuse are summarized in Table 1.Entries 2 and 3 describe coatings to make AN safer:the coating in entry 2 purports to make AN safer by preventing fuel oil from entering the pores of AN(al
56、though no mention is made of what happens when it is crushed),while entry 3 explicitly notes that the coal combustion-byproduct coating remains effective after crushing or attempts to separate AN by wet chemical means.Entries 4-11 describe blends to make AN less explosive.Physical countermeasures to
57、 prevent misuse include adding a coloring agent to prevent separation of AN and diluents by color screening(entry 6),and ensuring that prills(or grains)of AN and the diluents are the same size to prevent separation by a sized sieve(entry 10).Entries 9 and 10 use a well-known property of ANits hygros
58、copicity,or tendency to absorb water from the airto help complicate separation.In entry 9,urea double salts are added that form stable,non-hygroscopic fertilizers with AN,but,when crushed or added to water in an attempt at misuse,form hygroscopic urea-AN mixtures;the inclusion of a foaming agent in
59、the blend then makes a mess of any attempts to boil off the water.Entry 10 adds an organic polymer-encapsulated urea that forms a hydrogel with added or absorbed water if wet or dry methods of separation are attempted.Copyright 2021 American Chemical Society.All rights reserved10PatentDescription1WO
60、20024042719An ammonium sulfate nitrate composite fertilizer that is non-explosive.The material is made in such a way that it is mainly a 1:2 double salt of ammonium sulfate and AN(i.e.,(NH4)SO4.2(NH4NO3),with very little of the more hazardous 1:3 double salt or residual AN.Tests show that it is not
61、an oxidizer.2WO200310637720A coating for a fertilizer that prevents the infiltration of hydrocarbons(such as fuel oil)into the pores of fertilizer,thereby reducing its efficacy as an oxidizer in the production of an incendiary device.3US2008022309821A method of reducing the explosion potential of AN
62、 fertilizer by coating the fertilizer with a coal combustion by-product such as Class C fly ash,Class F fly ash,flue gas desulfurization waste,or atmospheric fluidized-bed combustion waste,and perhaps a binder.4WO201005360422A method to create stable AN composites by blending AN with substantially n
63、on-oxidizing compounds such as ammonium sulfate,ammonium phosphate,ammonium molybdate,ammonium hexafluorosilicate,calcium nitrate,calcium carbonate,magnesium nitrate,potassium nitrate,and potassium phosphate.5for humanitarian reasons,the inventors chose not to patent the formulation23A non-detonable
64、 fertilizer obtained by mixing iron sulfate with AN.The inventor(Fleming,then at Sandia National Laboratory)notes that iron prefers the nitrate,and ammonium prefers the sulfate,so that if fuel oil is added to attempt to make an explosive,the ions swap,and no explosion occurs.The mixture has an advan
65、tage for use in Afghanistan with its high pH soil because it acidifies the soil,unlike CAN,which makes soil more alkaline.6WO201403315924A method to make solid blends of urea-based particles either mixed with,or coated with,ammonium sulfate,and AN-based particles mixed with salts able to bind crysta
66、llization water such as magnesium nitrate,magnesium sulfate,or aluminum sulfate.The desiccant limits the formation of the liquid phase,and the ammonium sulfate avoids the formation of an unwanted urea AN double salt.The resulting blend is difficult to reprocess for explosive use.It also includes a c
67、oloring agent to make separation based on color screening impossible.7WO201507356125An ANbased fertilizer that includes stabilizers to prevent its use in ANFO-type explosives.The stabilizers included a layered double hydroxide,hydrocalumite,hydrotalcite,and hydroxyapatite,added in sufficient quantit
68、y to give a product with low specific impulse,when measured in a blast propagation test.8WO201510254426A non-explosive and non-flammable AN-based fertilizer made by mixing AN,urea,and formaldehyde in water,and then adding an acid to catalyze the polymerization of urea and formaldehyde,followed by dr
69、ying.9US20Uses the hygroscopicity of AN-based fertilizers to prevent misuse:if the fertilizer is crushed it will turn muddy,and if it is dissolved it will be harder to concentrate.The inventors claim an AN-based fertilizer composition that is non-hygroscopic under normal conditions,but be
70、comes hygroscopic after contact with water,e.g.by dissolving or grinding for potential misuse.The key ingredient is a urea double saltfor example,urea calcium nitratewhich forms a stable(non-hygroscopic)fertilizer with AN,but when dissolved forms a hygroscopic composition that is a challenge to dry.
71、A foaming agent is included in the composition to complicate attempts to boil away the moisture for misuse.10US929666318Another patent that uses hygroscopicity to advantage.A method is described to prevent the removal of calcium carbonate from CAN by adding an organic polymer to CAN that forms a hyd
72、rogel if water is added,making it impossible to remove the calcium carbonate,or a mixture that also includes encapsulated urea,so that if it is ground to a fine powder,the urea will absorb water,liquefying the mixture,and forming a hydrogel that preserves the non-detonable nature of CAN.The particle
73、s are the same size to prevent separation of the CAN using a sized sieve.11CNA composite fertilizer having AN and a phosphate,also containing an explosion-proof agent that includes a fire retardant,anti-explosion agents,hygroscopic agents,emulsifiers,dispersants,and anti-sticking agents.I
74、n addition,there is the broad class of NPK fertilizers(Section 5.3),which are three-component fertilizers providing nitrogen,phosphorus,and potassium and that contain relatively small amounts of AN;although non-explosive,they are subject to self-sustaining decomposition.29,30TABLE 1.SAFER AMMONIUM N
75、ITRATE FORMULATIONS.Copyright 2021 American Chemical Society.All rights reserved112.3 PATENTS RELATED TO AMMONIUM NITRATE AS FERTILIZERS The number of patent publications relating to AN fertilizers by country and year was extracted from the CAS content collection to establish an overview of the worl
76、dwide research efforts on AN as a fertilizer(Figure 3).China published significantly higher numbers of such patents in the years from 2001 to 2019,followed by the United States,the Russian Federation,and Germany.Figure 3.Number of patent publications yearly on ammonium nitrate fertilizers from the t
77、op four countries.20004200520062007200820092000002447566572844755873020885472912ChinaGermanyRussianFederationUSA Copyright 2021 American Chemical Society.All
78、 rights reserved123.1 PROPOSED MECHANISMS OF AMMONIUM NITRATE DECOMPOSITION AND EXPLOSIONAlthough the reactions of ammonium nitrate(AN)have been studied since the 1880s,31 a complete understanding of the exact mechanisms that take place during its thermal decomposition or combustion have yet to be r
79、ealized.The challenge of the study of AN lies in its inherent physical and chemical complexity as well as the dependence of its reactivity on ambient conditions,such as temperature,pressure,and water content.The presence of contaminants,which can decrease the stability of AN,further complicates the
80、study of AN reactions.Keeping these limitations in mind,the first step in the thermal decomposition of AN is the proton transfer between the ammonium cation and nitrate anion,as shown below(eq 1).32,33CHAPTER 3.THE EXPLOSIVE NATURE OF AMMONIUM NITRATE The proton transfer is endothermic.If AN decompo
81、ses and the diffusion of ammonia prevents further heat-generating reaction,the decomposition of AN will slow because of the absorption of heat.However,if the decomposition occurs in a closed space or in the middle of a sufficiently large pile of AN,the ammonia and nitric acid will stay near one anot
82、her,and subsequent reactions will give off heat and thus accelerate the decomposition of AN.(1)H+HHNNHHHHH+NOOO-NOOO-Copyright 2021 American Chemical Society.All rights reserved13CHAPTER 3.THE EXPLOSIVE NATURE OF AMMONIUM NITRATE Both radical and ionic pathways account for N2O as the major gaseous p
83、roduct in the thermal decomposition of AN.However,N2 and O2 are also produced.Although the exact mechanism is not known,the following equation is believed by some to be the main detonation reaction:(5)(6)NHHH.NHH.NHHOHH+H2ONON+-N.OO+.OH-NOO+NHH2NH4NO3 2N2 +O2 +4H2OThe hydroxyl radical can abstract a
84、 hydrogen atom from ammonia,yielding NH2 radical and water(eq 5).Upon reaction with the NH2 radical,NO2 is ultimately converted into nitrous oxide,N2O(eq 6).Above 290 C,radical mechanisms predominate following the dissociation of AN.37,38 Homolysis of the NO bond in nitric acid gives the hydroxyl ra
85、dical as well as NO2,a toxic gas responsible for the reddish-brown plume sometimes seen in AN explosions.(4)+N.OO+-+NOOHO.OHAt temperatures between 200 C and 290 C,the decomposition is hypothesized to follow an ionic pathway.34-36 Upon reaction with a proton source(NH4+,H3O+,or HNO3),nitric acid(HNO
86、3)affords the nitronium ion(NO2+)(eq 2),which subsequently oxidizes ammonia,giving N2O and H3O+(eq 3).(2)(3)+NHHHOHHH+NOO+NOOHO-NHHHHHHNH+HNHOOO-+NOO+Nitronium ionH2ONON+-NOO+NHHH Copyright 2021 American Chemical Society.All rights reserved3.2 WHY AMMONIUM NITRATE EXPLODES Explosives require fuel(so
87、mething that can be burned or oxidized)and an oxidant(something that can add oxygen to or remove electrons from other molecules)in confinement.AN contains both a fuel and an oxidizer in the same place:ammonia,which is generated by deprotonation of the ammonium ion,is a fuel,while nitrate is a strong
88、 oxidant.Their co-presence means that the fuel does not have to wait for oxygen or some other oxidant to cause combustion(“Any intimate mixture of a fuel and an oxidizer is a potential explosive”39).As the decomposition of AN is exothermic,once some of the AN breaks down,the released heat can initia
89、te explosions or detonations;for example,the combination of AN and fuel oil(ANFO)is used as an explosive.Compounds susceptible to explosion generally need to contain much more energy in their bonds than in the products they generate:the products of their reaction should be much more stable than the
90、starting materials.This is seen in AN,where the products of AN decomposition are much more stable than AN itself.Nitrate contains nitrogen-oxygen bonds;nitrogen and oxygen both have non-bonded electron pairs that repel each other and thus make the bonds between them weaker.The weaker bonds in nitrat
91、e make it easier to initiate reactions because breaking those bonds costs less energy.Decomposition and detonation of AN give off nitrogen oxides,nitrogen,oxygen,water,and large amounts of heat.40 Molecular nitrogen has a very stable triple bond,so reactions that can form nitrogen are highly exother
92、mic,and the formation of water also emits large amounts of energy.The energy heats the surrounding material,easing the movement of atoms to accelerate the decomposition,and expands the surrounding air,converting chemical energy to kinetic energy.Explosions also require that the products take up more
93、 volume than the reactants,either by generating so much heat that the products expand to a much larger volume than the volumes of the reactants or by creating gaseous products from solid or liquid starting materials.AN takes up a small volume(as solid or liquid)and produces gases(nitrous oxide,nitro
94、gen,oxygen,water vapor)that take up a much larger volume.In the decomposition of AN,between 2.5 and 3.5 moles of gases are formed for each mole of AN;40 at 200 C,the volume of the products is likely to be more than 1,000 times the initial volume of AN.The change in volume from solid to gas generates
95、 kinetic energy which,together with heat released by the decomposition,will damage the surroundings.14 Copyright 2021 American Chemical Society.All rights reserved14154.1 POLLUTANT GASESAn ammonium nitrate(AN)explosion produces massive amounts ofpollutant gases,such as nitrogen oxides(NOx),nitrogen
96、dioxide(NO2),nitrous oxide(N2O),ammonia(NH3),and others,which are harmful to thehealthofhumansand otherliving beings,and also cause environmen-tal damage.Nitrogen oxides(NOx),comprising NO and NO2,are common air pollutants and can irritate the respiratory system.Elevated levels of these pollutants c
97、aused by AN explosions are particularly concerning for people with respiratory conditions.Nitrogen dioxide(NO2),the gas that provides the characteristic reddish-brown color ofsmog as well as the cloud seen in the Beirut explosion,is extremely toxic and harmful to human health.Acute exposure to NO2 a
98、t a concentration of about 100 ppm can irritate skin and lungs;at higher concentrations,it can cause lung damage,edema,and death due to asphyxiation.41 Chronic exposure to NO2 may lead to respiratory complications such as airway inflammation and can exacerbate asthma.42-44 Furthermore,reactions ofNO
99、2and NOxwith water,oxygen,and other chemicals in the atmosphere form acid rain,leading to severe environmental damage.45 2NO2+H2O HNO3+HNO2Nitrous oxide(N2O),which is commonly known as“laughing gas”and is used as an anesthetic in surgery and dentistry,is another main product of AN decomposition.Nitr
100、ous oxide is a potent greenhouse gas:it has about 300 times the global warming potential of carbon dioxide(CO2)46 and has been implicated indamage to the ozone layer.47Ammonia(NH3)has a pungent odor,and readily dissolves in water.Humans can detect ammonia by odor at concentrations as low as 5 ppm,an
101、d detoxify ammonia in the liver at low concentrations.48 However,ammonia is irritating to the moist mucous membranes of the eyes,mouth,and respiratory tract of humans.49 U.S.OSHA(Occupational Safety and Health Administration)set an exposure limit stating that at concentrations of 25 ppm in the air,e
102、xposure time should be limited to under 8 hours;at concentrations of 35 ppm,the exposure time should be limited to within 15 minutes.50 Exposure to extremely high concentrations(500 ppm)of gaseous ammonia can result in lung damage or death.51 4.2 CARCINOGENS SUCH AS POLYCYCLIC AROMATIC HYDROCARBONS,
103、SILICA AND ASBESTOSIn addition to the toxic gases discussed above,airborne chemicals produced by the explosion can cause serious health problems.CHAPTER 4.HAZARDS DURING THE RECOVERY PHASE AFTER AMMONIUM NITRATE EXPLOSIONS Copyright 2021 American Chemical Society.All rights reserved16Some of the acc
104、idents discussed in this report were known to produce polycyclic aromatic hydrocarbons(PAHs)(produced from combustion),asbestos,and silica from fragmented building materials,which are carcinogens and can cause lung damage and exacerbate asthma.Polycyclic aromatic hydrocarbons(PAHs)are a large group
105、of organic compounds with two or more fused aromatic rings.They are combustion products of organic materials,mixtures of which contain multiple human carcinogens.Human exposure to PAHs takes place mainly by inhalation,ingestion,and topical absorption.When the PAHs are metabolized,the metabolites for
106、med bind to DNA.Formation of the PAH-DNA adducts is considered a necessary step in PAH-initiated carcinogenesis,as studied in experimental models and detected in human tissues.52According to the United States Environmental Protection Agency(EPA),16 PAHs are catalogued as“priority pollutants”because
107、of their toxicity,potential for human exposure,and frequency of occurrence in hazardous waste sites.53 They are also found at high concentrations at National Priorities List(NPL)hazardous waste sites.54,55Following the explosion in Beirut,monitoring equipment at the American University of Beirut reg
108、istered a sharp rise in particulate matter.The most worrisome constituents of the particulate matter are respirable crystalline silica(RCS)and asbestos.Silica and asbestos,which are still common building materials in many places,are inorganic substances composed largely of silicon and oxygen.Small f
109、ibers or particles can be generated during an explosion and remain in the air for an extended period,causing inhalation risks.The role of asbestos exposure in mesothelioma and lung cancer is well documented,but the dangers of exposure to RCS are less well recognized.Although only minimal exposure to
110、 asbestos is enough to cause harm,RCS requires greater exposure to cause conditions such as silicosis,lung cancer,and chronic obstructive pulmonary disease(COPD).56,57 Unfortunately,such high levels of exposure can easily occur because RCS is invisible and exposure causes no immediate symptoms.Accor
111、ding to the International Agency for Research on Cancer(IARC),asbestos and silica are established human lung carcinogens(Group 1).58,59 Silica exists in many different crystalline and non-crystalline(amorphous)forms.Quartz,the most common form of crystalline silica,is the second most common mineral
112、on the planet.RCS is fine enough to inhale deep into the bronchioles and alveoli causing seriousharm.Silica causes progressive granulomatous and fibrotic lung disease.The strong immunological response in the lung induced by silica particles and their toxicity to macrophages may promote not only fibr
113、osis but also cancer.The mechanism by which silica induces lung cancer is not clear,whether directly through effects on DNA or indirectly by promoting growth of already initiated tumor cells.Silica can cause chromosomal abnormalities in mammalian cells.There is recent evidence that lung tumors arise
114、 in areas adjacent to areas of fibrosis and that cytokines may play a role in carcinogenesis.60Asbestos refers to a variety of hydroxylated silicate minerals.Asbestos minerals are divided into two broad groups:serpentine and amphibole.Serpentine asbestos is called chrysotile,and the amphibole family
115、 includes crocidolite,anthophyllite,amosite,actinolite,and tremolite.Numerous studies have demonstrated that all types of asbestos have the potential to induce lung tumors and mesothelioma.60 Copyright 2021 American Chemical Society.All rights reserved17Figure 4.Number of published articles per year
116、 related to the hazards of polycyclic aromatic hydrocarbons,silica,or asbestos,according to the CAS content collection.Figure 4 shows the number of published articles per year according to the CAS content collection related to PAH,asbestos,or silica hazards.Recent official legal documents and guidan
117、ce may explain the increased interest in PAH hazards.In 2000,the EPAestablished ambient water quality criteria to protect humans from the carcinogenic effects of PAH exposure.Similarly,in 2003,WHO published guidance that set the unit risk of lung cancer of benzoapyrene(BaP)and other PAHs.On the othe
118、r hand,because of the recognized hazards of asbestos exposure and its reduced use in commerce,publications discussing it have declined in recent decades.6040200PAHYear19901995 20002005 20102015 2020Number of articles020AsbestosYear19901995 20002005 20102015 2020020Si
119、licaYear19901995 20002005 20102015 2020 Copyright 2021 American Chemical Society.All rights reserved18Figure 5.The top six countries in ammonium nitrate production.Data source:Food and Agriculture Organization of the United Nations http:/www.fao.org/faostat/en/#data/RFB5.1 WHY LARGE AMOUNTS OF AMMON
120、IUM NITRATE ARE STOREDAmmonium nitrate(AN)is widely used in fertilizers and mine explosives.As a nitrogen source,it has an NPK rating of 34-0-0,where the three numbers provide a measure of the relative content of nitrogen,phosphorus,and potassium.It is also a commonly used oxidant in many types of m
121、ining explosives.The total AN production worldwide was estimated to be 22 million tonnes in 2017,according to the data published by the Food and Agriculture Organization of the United Nations.Figure 5 shows the top six AN producers in 2015,2016 and 2017.CHAPTER 5.REGULATIONS ON AMMONIUM NITRATE STOR
122、AGE AND TRANSPORTATIONRussianFederationEgyptUzbekistanPolandUkraineUSAWorldwide Ammonium Nitrate Production(millions of tonnes)15 2016 2017 Copyright 2021 American Chemical Society.All rights reserved19Figure 6.Worldwide import amount of ammonium nitrate from 2002 to 2018 and top six coun
123、tries in ammonium nitrate import or export.Data source:Food and Agriculture Organization of the United Nations http:/www.fao.org/faostat/en/#data/RFBIn addition,data with the import and export AN amount were analyzed,results shown in Figure 6.The overall worldwide import amount seems to be stable,wi
124、th the top six AN importing countries being Brazil,Ukraine,United States,Peru,Australia and United Kingdom,and the top six exporting countries being the Russian Federation,Georgia,Lithuania,Bulgaria,United States and Sweden.These data give an estimate of how much AN is transported between countries,
125、but do not include AN transportation within countries.Ammonium Nitrate Import(millions of tonnes)1086420Year20009200320000018Leaders in Ammonium Nitrate Import 2018(millions of tonnes)USA1.03M3.59M0.44M0.45M0.35M0.34M0.36M0.41M0.34M0.34M0.32M0.3
126、1MLithuaniaUkraineGeorgiaBrasilRussianFederationPeruBulgariaAustraliaUSAUKSweedenAN has often been stored in large amounts in warehouses,because it was considered safe and does not easily burn when pure.However,it is a stronger oxidant than air and can accelerate combustionof other materials.When mi
127、xed with fuels,as in ANFO,explosions can readily occur.Once heated,AN decomposes to release large amounts of heat and gases.As discussed in Section 1.2,there have been nearly 40 AN disasters reported globally,causing more than 2,500 deaths.These tragedies highlight the dangers of AN,and justify the
128、need for diligent implementation of regulations worldwide,as well as increasing public awareness.Copyright 2021 American Chemical Society.All rights reserved20Country/AreaTitleDescriptionEuropean UnionDirective 82/501/EC(Seveso Directive I,1982),Directive 96/82/EC(Seveso Directive II,1996),DIRECTIVE
129、 2003/105/EC(amending Seveso Directive II),Directive 2012/18/EU(Seveso Directive III)The European Parliament and the Council of the European UnionEuropean Union Selected Tests Concerning the Safety Aspects of Fertilizers(1992)EFMA,IFA European Union Handbook for the Safe Storage of Ammonium Nitrate
130、Based Fertilizers(1992)EFMA,IFA European Union Best Available Technique Series for production of ammonium nitrate products(2000)EFMA,IFA Russian FederationGOST 2-2013-Ammonium nitrate.Specifications GOSTUnited StatesOSHA 29 CFR 1910.109(i)Storage of Ammonium Nitrate(2001)OSHACanadaAmmonium Nitrate S
131、torage Facilities Regulations(C.R.C.,c.1145)(2006,amended in 2015)CTCUnited KingdomAmmonium Nitrate Materials(High Nitrogen Content)Safety Regulations 2003HSEUnited KingdomStoring and handling ammonium nitrate(2001)HSEAustraliaSafe storage of solid ammonium nitrate(3rd ed.)(2013)W.A.Govt.,Dept.of Mi
132、nes and Petroleum Resources Safety*AustraliaStorage requirements for security sensitive ammonium nitrate(SSAN)(2020)Queensland Govt.,Dept.of Natural Resources,Mines and EnergyAustraliaHigh consequence dangerous goods(HCDG):Safety basics(2020)WorkSafe VictoriaChinaGB 2945-1989GB/T 2945-2017 Ammonium
133、nitrateAQSIQSACChina*GBF2020 52Notice of Further Strengthening Safety Management of Civil ExplosivesChina State CouncilTABLE 2.REGULATIONS AND GUIDELINES FOR STORAGE AND HANDLING OF AMMONIUM NITRATE.5.2 REGULATIONS AND RULES FOR AMMONIUM NITRATEPrevious disasters(Appendix 1)have heightened public aw
134、areness of the explosive nature of AN,and the consequences of its unsafe storage and*Abbreviation of Organizations:EFMA:European Fertilizer Manufacturers Association,BrusselsIFA:International Fertilizer Industry Association.ParisOSHA:Occupational Safety and Health AdministrationCTC:Canadian Transpor
135、t CommissionHSE:Health and Safety ExecutiveAQSIQ:General Administration of Quality Supervision,Inspection and QuarantineSAC:Standardization Administration of ChinaGOST:Russian Governmental Standard*GBF:Document issued by the general office of the State Council,China*Superseded by Dept.of Mines,Indus
136、try Regulations and Safety(DMIRS)in 2017 use.In response,many regulations,rules,and guidelines for AN,especially regarding its storage and handling,have emerged in different countries and areas in a bid to improve safety,as shown in Table 2.Copyright 2021 American Chemical Society.All rights reserve
137、d21The United States is one of the largest producers and consumers of AN and has suffered many tragedies involving AN(15 accidents listed in Appendix 1).As a result,a variety of regulations,rules,and guidelines have been published by the U.S.government,as listed in Figure 7 and Table 3.In addition,s
138、ome local governments or agencies also have guidelines related to AN.Figure 7.Timeline for ammonium nitrate-related accidents and regulations in the United States.4NFPA 490OSHA 29 CFR 1910.109(i)Guidance on the Ammonium Nitrate Storage Requirements in 29 CFR 1910.109(i)11 cases before 197
139、42009 Fire at a storage,Bryan,Texas1994 Explosion at the Port Neal,Iowa1988 ANFO explosion,Kansas City,Missouri2013Adair Grain(DBA West Fertilizer)Company explosion,West Texas Copyright 2021 American Chemical Society.All rights reserved22The primary U.S.regulations for AN are“OSHA 29 CFR 1910.109(i)
140、Storage of Ammonium Nitrate”,and the Memorandum of“Guidance on the Ammonium Nitrate Storage Requirements in 29 CFR 1910.109(i)”published in 2014 after the Adair Grain(DBA West Fertilizer)Company explosion(Appendix 1).In combination with other documents,the regulations may be summarized as follows:Ve
141、ntilation is the first requirement for safe storage of AN,because it can(1)prevent the accumulation of highly toxic off-gas products,such as ammonia and nitrogen oxides,and(2)remove hot gases from the structure to limit heating of the AN and reduce the risk of an explosion.For example,OSHA requires
142、that“Storage buildings shall have adequate ventilation or be of a construction that will be self-ventilating in the event of fire.”1910.109(i)(2)(iii)(b),and“Warehouses shall have adequate ventilation or be capable of adequate ventilation in case of fire.”1910.109(i)(4)(i)(a)for bulk storage.Ventila
143、tion also helps prevent AN agglomeration.AN is an extremely hygroscopic chemical and prills or grains will stick together after absorbing moisture.The powerful 1921 explosion in Oppau,Germany,was caused in part because AN and ammonium sulfate had agglomerated*Abbreviation of Organizations:NFPA:Natio
144、nal Fire Protection AssociationOSHA:Occupational Safety and Health AdministrationEPA:Environmental Protection AgencyATF:Bureau of Alcohol,Tobacco,Firearms,and ExplosivesIME:Institute of Makers of ExplosivesIAFC:The International Association of Fire ChiefsISEE:The International Society of Explosives
145、EngineersNSSGA:National Stone,Sand,and Gravel AssociationCRS:Congressional Research ServiceTFI:The Fertilizer InstituteARA:Agricultural Retailers AssociationCISA:Cybersecurity and Infrastructure Security Agency*Initially published in 2013 and republished in 2015TitleOrganization*YearNFPA 490(Hazardo
146、us Materials Code)NFPA 1974NFPA 400(The National Fire Protection Association Hazardous Materials Code)Chapter 11 on ammonium nitrateNFPA2016OSHA 29 CFR 1910.109(i)et seq.Storage of Ammonium NitrateOSHA2001Chemical Advisory:Safe Storage,Handling,and Management of Solid Ammonium Nitrate PrillsEPA-OSHA
147、-ATF 2013*,2015Safety and Security Guidelines for Ammonium NitrateIAFC-IME-ISEE-NSSGA 2013Regulation of Fertilizers:Ammonium Nitrate and Anhydrous AmmoniaCRS2013Safety and Security Guidelines for the Storage and Transportation of Fertilizer Grade Ammonium Nitrate at Fertilizer Retail FacilitiesTFIAR
148、A2014Safety and Security Guidelines for the Storage and Transportation of Fertilizer Grade Ammonium Nitrate at Fertilizer Retail and Distribution FacilitiesTFIARAResponsibleAg Inc.2018Chemical Facility Anti-terrorism Standards (CFATS)CISA2007Ammonium Nitrate Security Program(ANSP)CISAproposedTABLE 3
149、.REGULATIONS/GUIDANCE ABOUT AMMONIUM NITRATE IN THE UNITED STATES.Copyright 2021 American Chemical Society.All rights reserved23SAFESTORAGEISOLATIONVENTILATIONAVOIDANCE OF COMBUSTIBLE CONTAMINANTSFIRE PROTECTIONAMOUNT IN STORAGETEMPERATUREin a storage silo and formed a huge solid mass.Similarly,the
150、1942 Belgium explosion was also caused in part by an attempt to disaggregate an agglomerated pile of 150tonnes of AN with industrial explosives(Appendix 1).Therefore,OSHA requires that“Height or depth of piles shall be limited by the pressure-setting tendency of the product.However,in no case shall
151、the ammonium nitrate be piled higher at any point than 36 inches below the roof or supporting and spreader beams overhead.”1910.109(i)(4)(iii)(b).Reduced humidity and temperature can also inhibit AN agglomeration.Noncombustible and AN-resistant materials are required for use in storage and handling
152、areas,as stated in OSHA regulations 1910.109(i)(2)(iii)(d)and 1910.109(i)(4)(ii)(b).Galvanized iron,copper,lead,zinc,aluminum,and wood cannot be used due to either their combustibility or susceptibility to corrosion and reaction with AN.However,these materials can be used for storage bins if the bin
153、s are protected by an impermeable coating or cladding,such as two-part epoxy coatings,steel sheet cladding,or sodium silicate.Low temperature is required for safe storage of AN.OSHA requires that“Containers of ammonium nitrate shall not be accepted for storage when the temperature of the ammonium ni
154、trate exceeds 130 F.”1910.109(i)(3)(ii)(a)(54 C).Limits on the amount of AN stored are important for preventing tragic explosions.In the United States,the limit of bagged AN stored in a building or structure not equipped with an automatic sprinkler system is 2,270 tonnes(2,500 tons)1910.109(i)(7)(i)
155、.Many disasters involved amounts exceeding 2,270 tonnes(the 1947 Brest explosion,the 2020 Beirut explosion),but others involved only tens or hundreds of tonnes(the 2001 Toulouse explosion,the 2013 West Fertilizer Company explosion,and the 2015 Tianjin Port explosion).Meanwhile,in Europe,though the E
156、uropean Union does not mandate limits on the amounts of AN stored,the stringency of regulations in the Seveso Directive acts to limit the amount of dangerous substances present within an establishment.Fire protection is essential for AN storage.Fire has played a significant role in many accidents in
157、volving AN.Accordingly,strict fire protection measures are necessary for AN storage.The requirements for water sprinkler systems and fire control devices(such as fire hoses,portable fire extinguishers,water supplies,and fire hydrants)are clearly stated in OSHA regulations 910.109(i)(7)(i)and 1910.10
158、9(i)(7)(ii)(a)&(b).In summary,safe AN storage requires ventilation,isolation from combustible materials,temperature control,control of the amount in storage,fire protection,and avoidance of combustible contaminants(Figure 8).Figure 8:Ammonium nitrate safe storage guidelines.Copyright 2021 American C
159、hemical Society.All rights reserved24*NPK rating:relative content of nitrogen,phosphorus,and potassium*RMP:Risk Management Plan625.3 ALTERNATIVE NITROGEN FERTILIZERSAlthough AN is an important fertilizer because of its high nitrogen content,its explosive hazards limit its applications and it is even
160、 banned in some areas.Reducing the concentration of AN,finding alternative compounds,and developing safer forms may help to increase the safety of nitrogen fertilizers.Table 4 lists alternative nitrogenous fertilizers with their NPK ratings(defined above in comparison to AN).Unfortunately,the altern
161、ative with the highest nitrogen content is anhydrous ammonia,which is a gas at ambient temperature and is toxic.Other alternatives with high nitrogen content,such as ammonium hydroxide solutions and urea,are volatile.Mixing high nitrogen content fertilizers with other macronutrients to form NPK mixt
162、ures reduces the explosive risk while still meeting plant nutritional requirements(Table 5).Fertilizer Formula(CAS Registry Number)NPK rating*108CommentAmmonium nitrateNH4NO3(6484-52-2)34-0-0High nitrogen content with explosive riskAnhydrous ammoniaNH3(7664-41-7)82-0-0Pressurized gas,RMP*-regulated
163、substance with a threshold of 10,000 lbs,109 regulated as Dangerous Goods for transportation.110 Aqua ammoniaNH4OH(1336-21-6)(16-25)-0-0Volatile,RMP-regulated substance with a threshold of 20,000 lbs.109UreaCO(NH2)2(57-13-6)46-0-0High nitrogen content,volatileAmmonium sulfate(NH4)2SO4(7783-20-2)21-0
164、-0Non-volatile,low nitrogen contentDiammonium phosphate(NH4)2HPO4(7783-28-0)18-46-0Contains phosphorusMonoammonium phosphate NH4H2PO4(7722-76-1)11-48-0Contains phosphorusPotassium nitrateKNO3(7757-79-1)13-0-44Contains potassium,stableSodium nitrateNaNO3(7631-99-4)16-0-0StableCalcium cyanamide CaCN2(
165、156-62-7)21-0-0Contains calciumCalcium nitrateCa(NO3)24H2O(13477-34-4)15-0-0Contains calciumTABLE 4.COMPARISON OF AMMONIUM NITRATE WITH ALTERNATIVE NITROGENOUS FERTILIZERS Copyright 2021 American Chemical Society.All rights reserved25Urea has been explored as another alternative as its high nitrogen
166、 content and low cost make it an attractive candidate.However,urea fertilizers are volatile,so many slow-release formulations have been developed.61-64 Other slow-release nitrogen fertilizers,such as modified lignins65 and hydrogels,66 have also been developed.Fertilizer Formula(CAS Registry Number)
167、NPK rating*61CommentCalcium nitrate/urea(Cal-Urea)Ca(NO3)2+4CO(NH2)2(5124-41-4)34-0-0Contains calcium;urea volatilizes from the soil before it is all used by the plants.Ammonium nitrate sulfateNH4NO3+x(NH4)2SO4(1628327-53-6)N.A.Reduced explosive risk compared to ANUrea/ammonium nitrate(N-SOL or UAN
168、solutions)CO(NH2)2+NH4NO3(15978-77-5)(19-32)-0-050%nitrogen is volatileAmmoniated superphosphateN.A.(12-17)-(22-35)-0Contains phosphorusAmmonium phosphate nitrate NH4H2PO4+xNH4NO3(57608-40-9)N.A.Contains phosphorusAmmonium phosphate sulfate NH4H2PO4+x(NH4)2SO4(86438-07-5)N.A.Contains phosphorusAmmon
169、ium polyphosphateN.A.(68333-79-9)N.A.Contains phosphorus,liquidNitric phosphateN.A.(12-17)-(22-35)-0Contains phosphorusTABLE 5.FERTILIZER MIXTURES CONTAINING NITROGEN Copyright 2021 American Chemical Society.All rights reservedDespite associated safety concerns,ammonium nitrate(AN)remains an importa
170、nt fertilizer worldwide as it is effective,inexpensive,and easy to manufacture.However,as has been highlighted once more by the Beirut incident,ANs susceptibility to fire and explosion when contained,contaminated,or located near flammable substances present significant risks.The development of impro
171、ved AN formulations,better management of the handling of AN,diligence in isolation and fire prevention in the storage of AN,and better general awareness of the associated risks of AN are crucial in preventing further disasters.The associated risks of AN are significantly increased when large quantit
172、ies are stored in populated areas for an extended period of time.The recent explosion in Beirut triggered a dramatic increase in interest concerning the safety aspects of AN.A review of the historical accidents involving AN around the world showed that they mostly occurred during storage or transpor
173、tation.A lack of awareness of how to safely handle and store AN is one of the common factors that cause these tragic accidents.Therefore,the need for safer formulations of AN and better strategies and training for preventing accidents and misuse is clear.As analysis of patent literature shows,better
174、 formulations are in development;however,there is yet to be a suitable,accessible alternative.The market for AN is expected to grow at 4.90%annually over the next seven years.67 There is therefore a clear commercial opportunity to develop a safe,affordable alternative for AN.However,the development
175、of a suitable alternative is likely to take several years,putting pressure on governing bodies worldwide to implement and enforce adequate AN safety regulations.In addition,improved enforcement and regulation of AN handling by governments in combination with stewardship of AN by its manufacturers wi
176、ll likely be necessary.Improved management of the AN supply chain can also reduce the use of AN in improvised explosives.Further enforcement needs to be focused on longer time scales,and consistently applied worldwide.Overall,this report may serve to educate the public for promoting the awareness of
177、 AN safety.It may also provide a useful resource to scientists in the AN research field,as well as business leaders in the AN industry,for their efforts to further improve the safety of AN.CHAPTER 6.SUMMARY AND PERSPECTIVES2627 Copyright 2021 American Chemical Society.All rights reserved27DateCountr
178、yLocationDeathsAN(tonnes*)OccurrenceDetailsACCIDENTS DURING STORAGE19162-AprUnited KingdomFaversham,Kent115630StorageA fire spread to 25 tons of TNT and 700 tons of AN stored at a factory in Uplees,Faversham which then exploded.7219241-MarUnited StatesNixon,New Jersey 202StorageA warehouse containin
179、g 4,800 pounds of AN at the Nixon Nitration Works was destroyed by a fire and several large ex-plosions.The explosiveness of the product may have been enhanced by impurities present in the nitric acid which had been used previously for producing TNT.7319405-AugFranceMiramas0240Storage(warehouse)240
180、tonnes of AN exploded from the impact of a shell thrown from a fire in a nearby munitions train.74194726-AugUnited StatesPresque Isle,Maine0220StorageSpontaneous heating in a stack of mixed fertilizer destroyed 240 tons of AN stored at a plant of the A.W.Higgins Company.751947CanadaSt.Stephen,New Br
181、unswick0360Storage(plant)Fire at the Summers Fertilizer Company(St.Stephen,New Brunswick)burned 400 tons of stored AN;no explosion occurred.7519639-JanFinlandOulu1010StorageAN used for fertilizer and explosives at the Typpi Oy industrial site in Oulu caught fire and exploded.76198829-NovUnited State
182、sKansas City,Missouri623(ANFO*)Storage(trailer)More than 25 tons of AN with fuel oil(ANFO)(to be used for blasting)exploded at a construction site in Kansas City,Missouri.Five people were convicted of arson for the explosions.7719942-AugPapua New GuineaPorgera Gold Mine1180(ANE)Storage(plant)Two exp
183、losions occurred at a sensitized AN emulsion(ANE)plant near the Porgera Gold Mine in Papua New Guinea.The initial explosion involved a few tonnes of explosive;the subsequent fire ignited about 80 tonnes of the ANE causing a larger explosion with a mushroom cloud.78199413-DecUnited StatesPort Neal,Io
184、wa4 N.A.Storage(plant)Two explosions at the Port Neal,Iowa,AN processing plant operated by Terra Industries caused the release of 5,700 tons of anhydrous ammonia that continued for 6 days after the explosions.Nearby groundwater was contaminated.79,80APPENDIX 1.LIST OF AMMONIUM NITRATE DISASTERS.6-9
185、Copyright 2021 American Chemical Society.All rights reserved28DateCountryLocationDeathsAN(tonnes*)OccurrenceDetailsACCIDENTS DURING STORAGE19986-JanChinaXingping,Shanxi2225Storage(plant)An accident caused the explosion of 27.6 tons of AN liquor contained at the Xinghua Fertilizer Company.81,82200121
186、-SepFranceToulouse31200-300StorageA warehouse at the AZF(Azote de France)fertilizer factory(Toulouse,France)exploded.The warehouse contained off-specification granular AN which was stored flat and separated by partitions.The cause of the explosion was not determined.8320031-JanSpainCartagena,Murcia0
187、 N.A.Storage(warehouse)AN fertilizer in the storage facility of Fertiberia(Cartagena,Spain)underwent self-sustained decomposition and caught fire.Mechanical removal of unburned AN controlled the fire.7420032-OctFranceSaint-Romain-en-Jarez03-5StorageA barn in Saint-Romain-en-Jarez(Loire)containing 3-
188、5 tonnes of bagged AN caught fire.84200930-JulUnited StatesBryan,Texas0 N.A.Storage(warehouse)The El Dorado Chemical Company in Bryan,Texas,a company processing AN into fertilizer,caught fire.85201317-AprUnited StatesWest,Texas15240StorageA fire(determined to be arson)at a fertilizer company in West
189、,Texas,caused AN stored there to explode.The explosion destroyed roughly 80 homes and a middle school.86,87201512-AugChinaPort of Tianjin173800Storage(warehouse)Nitrocellulose stored at a Port of Tianjin hazardous goods warehouse spontaneously combusted,igniting a fire which triggered the detonation
190、 of AN stored nearby.88,8920204-AugLebanonBeirut200-3002,750Storage(plant)Fire broke out in a Port of Beirut(Lebanon)warehouse containing 2,750 tonnes of AN seized from an abandoned ship impounded in 2014.At least 6,000 people were injured and nearly 300 people died.90,91DateCountryLocationDeathsAN(
191、tonnes*)OccurrenceDetailsACCIDENTS DURING TRANSPORTATION192014-AprilUnited StatesBrooklyn,New York01,919/882Transportation(cargo ship)Fire broke out on the steamer Hallfried while discharging cargo,which included 1,919 tonnes of AN in casks.Although the fire was intense and 882 tonnes of the AN were
192、 destroyed,no explosion occurred.75 Copyright 2021 American Chemical Society.All rights reserved29DateCountryLocationDeathsAN(tonnes*)OccurrenceDetailsACCIDENTS DURING TRANSPORTATION19253-MayUnited StatesMuscle Shoals,Alabama0 Transportation440 barrels of AN caught fire and exploded during shipping
193、from a warehouse in Muscle Shoals,Alabama.The barrels had been stored in a warehouse with varying humidity for 6 years,and were likely ignited by friction of the barrels with their nitrate-impregnated paper linings.92194716-AprUnited StatesTexas City5812,100+870Transportation(cargo ship)The cargo sh
194、ip Grandcamp was being loaded when a fire was detected in the hold:2,300 tons of AN in sacks were already aboard.The ship exploded,setting fire to another vessel,250 m away,which contained 1,050 tons of sulfur and 960 tons of AN.93,94194728-JulFranceBrest291,700-3,309Transportation(cargo ship)The No
195、rwegian cargo ship Ocean Liberty was loaded with 3,309 tonnes of AN and various flammable products when it caught fire.Pumping pressured steam into the sealed hold did not stop the fire;the ship exploded while being towed from the harbor.95,96195323-Jan-Red Sea0 N.A.Transportation(cargo ship)The Fin
196、nish cargo ship Tirrenia caught fire while carrying AN.The fire could not beextinguished with steam,and the ship was abandoned before it exploded.9719597-AugUnited StatesRoseburg,Oregon144.1Transportation(truck)A truck carrying dynamite and 4.5 tons of AN caught fire and exploded.A number of blocks
197、of downtown Roseburg,Oregon,were destroyed by the explosion.98,99196017-DecUnited StatesTraskwood,Arkansas0140-180Transportation(train)A train carrying AN,fuel oil,and nitric acid derailed.The AN did not explode,but reac-tion of the nitric acid with fuel oil caused anexplosion which scattered the AN
198、 at the crash site.100197230-AugAustraliaTaroom,Queensland311Transportation(truck)An electrical fault in a truck carrying 11 tonnes of AN caused a fire and explosion north of the Queensland town of Ta-room.101200418-FebIranNeyshabur300399Transportation(train)A train carrying sulfur,AN,cotton,and oil
199、 derailed and exploded,killing 300 people.102,103 Copyright 2021 American Chemical Society.All rights reserved30 Copyright 2021 American Chemical Society.All rights reservedDateCountryLocationDeathsAN(tonnes*)OccurrenceDetailsACCIDENTS DURING MANUFACTURING/PROCESSING191614-JanUnited StatesGibbstown,
200、New Jersey11.81Manufacturing4,000 pounds of AN exploded in an evaporating pan of the Repauno works of the du Pont Co.The explosion may have been caused by overheating of the AN by a clogged air lance.110191615-SepUnited StatesOakdale,Pennsylvania61.36ManufacturingAt Aetna Chemical Co.,3,000 pounds o
201、f AN exploded while being concentrated by evaporation.Impurities in the nitric acid used to produce the AN were proposed as the cause.111DateCountryLocationDeathsAN(tonnes*)OccurrenceDetailsACCIDENTS DURING TRANSPORTATION20049-MarSpainBarracas225Transportation(truck)A truck carrying 25 tonnes of AN
202、fertilizer exploded after a traffic accident.104200424-MayRomaniaMihileti,Buzu1820Transportation(truck)A truck carrying 20 tonnes of AN over-turned and caught fire.The explosion left a crater 6.5 m deep and 42 m in diameter.105200422-AprNorth KoreaRyongchn162 Transportation(train)A freight train car
203、rying AN exploded,in Ryongchon,destroying the train station and nearly 8,000 homes in the city;most buildings within 500 m of the explosion site were damaged.1062007SpainEstaca de Bares0400Transportation(cargo ship)2,600 tonnes of NPK fertilizer*(of 6,000 tonnes)carried on the ship Ostedijk underwen
204、t self-sustained decomposition and burned for 11 days.NPK fertilizer contains about 15%AN.10720079-SepMexicoMonclova,Coahuila2822(ANFO)Transportation(truck)A pickup truck crashed into a trailer containing 22 tonnes of ANFO,causing a fire in the trailer and a large explosion.10820145-SepAustraliaWyan
205、dra,Queensland056Transportation(truck)A truck carrying 56 tonnes of AN exploded due to a traffic accident.The explosions sent debris up to 2 km from the crash site.10931DateCountryLocationDeathsAN(tonnes*)OccurrenceDetailsACCIDENTS DURING MANUFACTURING/PROCESSING192126-JulGermanyKriewald1930Processi
206、ngMining explosives were used in an attempt to dislodge 30 tonnes of AN that had aggregated in two wagons,exploding the wagons instead.192121-SepGermanyOppau561450ProcessingAttempted disaggregation of a 50:50 mixture of AN and ammonium sulfate stored at a BASF plant in Oppau caused a massive explosi
207、on.Only 450 tonnes of the AN exploded,out of 4,500 tonnes of fertilizer in the pile.112,1131925United StatesEmporium,PennsylvaniaN.A0.2Manufacturing500 pounds of AN exploded during evaporation.8194229-AprBelgiumTessenderlo189150ProcessingAttempted disaggregation of a pile containing 150 tonnes of AN
208、 with industrial explosives caused an explosion.1141944United StatesMilan,Tennes-see4N.A.ManufacturingExplosion during evaporation(AN contami-nated with oil and further sprayed with oil-air mixture from a broken compressor).8*One tonne,sometimes called a metric ton,is equal to 1,000 kg,as opposed to
209、 one ton,which is 2,000 lb.*ANFO:ammonium nitrate mixture with fuel oil*NPK fertilizer:Nitrogen-phosphorus-potassium fertilizer Copyright 2021 American Chemical Society.All rights reserved32REFERENCES1.Ilyushina,M.;Polglase,K.;Younes,A.A Russian ships cargo of dangerous ammonium nitrate was stranded
210、 in Beirut port for years.https:/ Sept.18,2020).2.2020 Beirut explosion.https:/en.wikipedia.org/wiki/2020_Beirut_explosion(accessed Sept.18,2020).3.Hubbard,B.,Abi-Habib,M.,El-Naggar,M.,McCann,A.,Singhvi,A.,Glanz,J.White,J.How a Massive Bomb Came Together in Beiruts Port.New York Times,Sept.9,2020.ht
211、tps:/ deadly history of ammonium nitrate,the explosive linked to the Beirut blast.https:/ Sept.18,2020).5.Rhodes,R.Tongues of Fire.The Making of the Atomic Bomb,1st edition,Touchstone:New York,NY,1988;p.729.6.Wikipedia.Ammonium nitrate.https:/en.wikipedia.org/wiki/Ammonium_nitrate(accessed Sept.18,2
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266、/wiki/Tessenderlo_Group(accessed Sept.23,2020)ipedia.org/wiki/Oppau_explosion(accessed Sept.23,2020)37 Copyright 2021 American Chemical Society.All rights reserved38CAS RESEARCH WORKING TEAMPROJECT PLANNING Manuel Guzman Gilles P.Georges Carmin J.Gade Michael Dennis Cynthia D.Casebolt Dawn L.George
267、Laura Czuba Angela ZhouADVISORY BOARD Adam R.Sanford Albert L.Ihochi Catherine Saveson Carmin J.GadeAUTHORS Rumiana Tenchov(Biophysics)Robert Bird(Organic Chemistry)Allison E.Curtze(Chemistry)Min Wang(Applied Chemistry)Roger Grev(Theoretical Chemistry)Zachary J.Baum(Inorganic Chemistry)Xiang Yu(Poly
268、mer Chemistry)Angela Zhou(Molecular Pharmacology and Toxicology)PUBLICITY AND PROMOTION Peter Jap Cristina C.Tomeo Carmin J Gade Caroline MaACKNOWLEDGEMENT We want to give special thanks to Dr.Harry J.Elston and Kimberly J.Brown for reviewing this report and providing critical feedback.We are also g
269、rateful to Naum Sayfullin,Yingqi Wu,Mark Grabau and Chris Aultman,for their help in data visualization and Susan Jervey and Anne Coghill for their careful editing and proofreading.Copyright 2021 American Chemical Society.All rights reserved39 Copyright 2021 American Chemical Society.All rights reser
270、ved 2021 American Chemical Society.All rights reserved.CASGENENGWHP7CAS is the Scientific Information Solutions Division of the American Chemical Society.We partner with R&D organizations globally to provide actionable scientific insights that help them plan,innovate,protect their innovat
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