Guidance for UN Classification of Ammonium Nitrate Based Substances (2006)

e u r o p e a n f e r t i l i z e r m a n u f a c t u r e r s a s s o c i a t i o n

GUIDANCE FOR UN CLASSIFICATION OFAMMONIUM NITRATE BASED SUBSTANCES

2006

Copyright 2006-EFMA

EUROPEAN FERTILIZER MANUFACTURERS’ ASSOCIATION

AVE. E. VAN NIEUWENHUYSE 4B-1160 BRUSSELS

BELGIUM

C O N T E N T S

1

A M M O N I U M N I T R A T E B A S E D S U B S T A N C E S

1. INTRODUCTION 2

2. SCOPE AND STRUCTURE OF GUIDANCE 4

3. LOGIC DIAGRAM 5

4. OFFICIAL TEXT FROM THE ORANGE BOOK 8

4.1. Main Substances 8

4.2. Special Provisions (SP) 9

5. NOTES TO LOGIC DIAGRAM (FIGURES 1 AND 2) 11

6. REFERENCES 14

APPENDIX 1 15

APPENDIX 2 22

Prepared by EFMA – May 2006

DISCLAIMER:The information and guidance provided in this document is given in goodfaith. EFMA, its members, consultants and staff accept no liability for

any loss or damage arising from the use of this guidance.

1 . I N T R O D U C T I O N

2


A number of AMMONIUM NITRATE BASED ‘SUBSTANCES’are listed as dangerous goods in the United Nations’ publication,Recommendations on the Transport of Dangerous Goods ModelRegulations (Ref. 1), which is popularly known as the Orange Book.They fall in different Classes depending on their compositions andpotential hazards. Most of the ammonium nitrate based products areclassified based on their composition for reasons of past experienceand knowledge. Those which are not covered in this way may besubject to a testing regime.

The number of fertilizer mixtures, which are produced to meet theagricultural needs, is large and, consequently, considerable amount oftesting would need to be carried out, if a test-based system ofclassification were to be applied. In order to avoid such unnecessarytesting and to get a consistent approach, the classification of ANproducts is sensibly based on composition.

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The composition components specified in the UN model regulationsare AN, combustible substances, total combustible/organic materialand other added materials, if any, e.g. inert diluents and nutrientsource materials such as phosphate and potash type (potassium saltssuch as KCl, K2SO4 and KNO3). Clearly, such a composition-basedsystem inevitably has to take a broad and pragmatic approach; itcannot cover all possible combinations in a precise way.

In EU for packaging and labelling purposes the Classification,Packaging and Labelling Directive is applied. Its oxidising capacity testis different from the one in the UN scheme. In future the UNtransport and various other schemes (including the EU’s CPL system)will be harmonised into a single global system. The present UNsystem for solid oxidisers is expected to be used in the global scheme.

In order to provide a common understanding and a practical approachto the classification used in the Orange Book relating to AN fertilizers,EFMA has prepared this guidance for its members. It is based on theindustry’s established practices over many years, its interpretation ofthe intended controls, its understanding of the potential hazards andknowledge of the wide range of products produced.

2 . S C O P E A N D S T R U C T U R E O F G U I D A N C E

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This guidance considers solid products containing ammonium nitrateas the main ingredient. It does not cover products which containmicronutrients such as Mn, Cu and Zn; they may have to be classified(additionally, where appropriate) as marine pollutants (class 9, UN No.3077) depending on the concentration of the micronutrients.

The guidance uses logic diagrams to cover all the relevant combinationsor compositions based on AN. The official text in the Orange Book,which describes the entries for the above products and the associatedSpecial Provisions, is included in section 4 to facilitate the process.

Notes to the diagrams are given, in section 5, to provide appropriatesupplementary information to some of the boxes, where appropriate.

In some countries the competent authorities have given derogationsfrom classification to certain compositions e.g. mixtures of AN (up to80%) with calcium sulphate. Such exceptions are outside the scope ofthis guidance.

3 . L O G I C D I A G R A M

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The logic diagram is split into two figures, 1 and 2. It uses the ANcontent as the main parameter. The second level parameter is based onthe nature and concentration of the other ingredients. The fertilizersare categorised as compounds (i.e. NP, NK or NPKs) or straight-Ntypes (i.e. those containing only nitrogen as the nutrient). The mainsource of nitrogen here is AN but other nitrates such as potassiumnitrate, sodium nitrate and calcium nitrate can also be potentialsources.

Three examples of the application of this diagram for differentfertilizer compositions are given in appendix 1.

It is important to note that the EU Resistance to Detonation Test isnot part of the UN classification system. In the EU, the FertilizerRegulations (EC No. 2003/2003) require most high AN fertilizers tosatisfy the EU Resistance to Detonation Test.

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Does the product contain

both NO3- and NH4

+ ionsRef SP186 (Note 1)

Not consideredin this scheme

Is AN ≥ 90%Consider UN 0222

Class 1 Is total combustible/organic ≤ 0.2% C?

(Note 2)

Consider UN 1942 Class 5.1

Ref SP 306

Not considered in this scheme

UN 2067 Class 5.1

Ref. SP 306

Is the product a compound fertilizer?

(Note 5)

Capable of self-sustaining

decomposition? Ref SP 193

UN 2071Class 9(Note 9)

Not classified as hazardous

(Note 9)

No

Yes No

Yes

Yes

No

No

No

Figure 2

NoYes

Yes

Yes

Yes

No

Is added matter, if any,inert towards AN?Ref SP 307 (a)

(Note 4)

Yes

No

Is it essentially pure ammonium nitrate?

(Note 3)

AN > 70%Ref SP 307 (b)

(Note 2)

Figure 1

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mixture with Ca/Mgcarbonates?

(Note 4)

AN > 80%Ref SP 307 (b)

(Note 2)

Not classifiedas

hazardous

Yes

containing mixturesof AN and AS?Ref SP 307 (c)

(Note 4)

AN > 45%

AN + AS > 70%?(Note 2)

No

No

UN 2067 Class 5.1

Ref. SP 306

No

Mixture with other inorganic materials?

Ref SP 307 (b)(Note 7)

AN > 70%?(Note 2)

No

Not classifiedas

hazardousNot classifiedin this scheme

(Note 8)

No

AN < 70% See Note 6

Yes

Yes

No

Yes

Not classifiedas hazardous

No

Yes

Yes

No

Yes

UN 2067Class 5.1

Ref. SP 306Yes

Straight nitrogenproduct, < 90% AN

(Note 5)

From Figure 1

Figure 2

4 . O F F I C I A L T E X T F R O M T H E O R A N G E B O O K ( R E F . 1)

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4.1 Main Substances

Ammonium nitrate based main solid products considered here arelisted below with their UN numbers, shipping names, class and specialprovision numbers. The official text is shown in italics.

UN 0222: Ammonium Nitrate – Class 1.1DAmmonium nitrate with more than 0.2% combustible substances,including any organic substance calculated as carbon, to the exclusion ofany other substance.

UN 1942: Ammonium Nitrate – Class 5.1Ammonium nitrate with not more than 0.2% total combustible material,including any organic substance calculated as carbon, to the exclusion ofany other added substance. Special provision 306.

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UN 2067: Ammonium Nitrate Based Fertilizer – Class 5.1(Description is given in SP 307.)Special provisions 186, 306 and 307.

UN 2071: Ammonium Nitrate Based Fertilizer – Class 9(Description is given in SP 193.)Special provisions 186 and 193.

4.2 Special Provisions (SP)

SP 186In determining the ammonium nitrate content, all nitrate ions for whicha molecular equivalent of ammonium ions is present in the mixture shallbe calculated as ammonium nitrate.

SP 193This entry may only be used for uniform ammonium nitrate basedfertilizer mixtures of the nitrogen, phosphate or potash type, containingnot more than 70% ammonium nitrate and not more than 0.4% totalcombustible/organic material calculated as carbon or with not more than45% ammonium nitrate and unrestricted combustible material.Fertilizers within these composition limits are only subject to theseRegulations when transported by air or sea and are not subject to theseRegulations if shown by a Trough Test (see Manual of Tests and Criteria,Part III, sub-section 38.2) not to be liable to self-sustainingdecomposition.

(It should be noted that some model regulations apply therequirements of UN 2071, even if the Trough Test does not showself-sustaining decomposition behaviour) (see Note 9).

SP 306This entry may only be used for substances that do not exhibit the explosiveproperties of Class 1 when tested in accordance with Test Series 1 and 2of Class 1 (see Manual of Tests and Criteria, Part I).

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SP 307This entry may only be used for uniform mixtures containing ammoniumnitrate as the main ingredient within the following composition limits:

a) Not less than 90% ammonium nitrate with not more than 0.2% totalcombustible/organic material calculated as carbon and with addedmatter, if any, which is inorganic and inert towards ammoniumnitrate; or

b) Less than 90% but more than 70% ammonium nitrate with otherinorganic materials, or more than 80% but less than 90%ammonium nitrate mixed with calcium carbonate and/or dolomiteand not more than 0.4% total combustible/organic materialcalculated as carbon; or

c) Nitrogen type ammonium nitrate based fertilizers containing mixturesof ammonium nitrate and ammonium sulphate with more than 45%but less than 70% ammonium nitrate and not more than 0.4% totalcombustible/organic material calculated as carbon such that the sumof the percentage compositions of ammonium nitrate and ammoniumsulphate exceeds 70%.

5 . N O T E S T O L O G I C D I A G R A M ( F I G U R E S 1 A N D 2)

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The following notes are intended to provide guidance andexplanation; they must not be interpreted or used as strict or legaldefinitions/requirements. The note numbers are as given in the logicdiagram.

1. With reference to SP186, ammonium ions (NH4+) and nitrate

ions (NO3-) may originate from ammonium nitrate itself or from

different materials (e.g. ammonium phosphates and potassiumnitrate). The method of calculating ammonium nitrate content isillustrated by examples in appendix 2. Where the nitrate contentis well in excess (e.g.>10%; this figure was specified in theeleventh/1999 and earlier editions of IMO Code, Ref. 2) of theammonium content consider classification due to the nitrate, asappropriate. For example, if other nitrates, such as sodium nitrate,are incorporated, reference should be made to other UN numbersunder which such products may be classified e.g. UN1477.

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2. The total content of combustible and organic substances must belimited as follows:

Composition Total combustible/organic materialcalculated as carbon

AN ≥ 90% 0.2%

AN > 45% (& <90%) 0.4%

AN ≤ 45% for unrestrictedcompound fertilizers

Note: elemental sulphur is combustible and can react vigorouslywith AN; it must not be added.

If the above limits are exceeded, the fertilizer will not be acceptedfor carriage in some model regulations except under theconditions applicable to Class 1 (Ref. 3).

3. Ammonium nitrate comes in different forms depending upon itsintended use. Ammonium nitrate in crystalline, porous prill orgranular form is mainly used for industrial applications such asbase material for explosives (UN1942). Ammonium nitratefertilizers of type UN 2067 are uniform mixtures (in prill orgranular form) and contain ammonium nitrate as mainingredient.

4. In practice, inert towards AN means that the material does notenhance the hazardous properties of the AN. It is commonpractice in the fertilizer industry to incorporate additives (e.g.magnesium nitrate, aluminium sulphate, ammonium sulphate)up to about 5% by weight in total, in order to improve thephysical characteristics such as caking behaviour, hardness andthermal stability against temperature cycling without adverselyaffecting the hazardous properties.

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5. Definition of straight and compound fertilizer from CEN (EN12944-1: 1999):

Straight fertilizerQualification generally given to a nitrogenous, phosphatic orpotassic fertilizer having a declarable content of only one of theprimary nutrients

Compound fertilizerFertilizer, obtained chemically or by blending or both, having adeclarable content of at least two of the primary nutrients.

6. Mixtures containing AN and AS, with ≥70% AN are notconsidered suitable as fertilizers due to their dangerous properties.They are not described in the classification system in the “OrangeBook”. However, as stated in note 4, small amounts of AS (up toabout 5%) are acceptable.

7. Typical other inorganic materials include calcium sulphate, clayand kieselguhr.

Note: such materials should be compatible with AN. Reactivematerials such as copper salts and sulphur should not be used.

8. Where this scheme fails clearly to identify the appropriateclassification of any formulation e.g. where high levels ofcombustible/organic substances or incompatible inorganicsubstances are present the advice of your competent authorityshould be sought.

9. In ADNR regulations (Ref. 4), when transporting in bulk,product which is not capable of self-sustaining decomposition(SSD) is classified as UN 2071, requiring the corresponding rulessuch as the provision of safety equipment to be applied.

6 . R E F E R E N C E S

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1. UN Recommendations on the Transport of Dangerous Goods.Model Regulations. (2005), Fourteenth edition, United Nations,ISBN 92-1-139106-7.

2. IMO, International Maritime Dangerous Goods Code (IMDG) .Two volumes. IMO Publications, London.

3. European Agreement Concerning the International Carriage ofDangerous Goods by Road, ADR 2005, page 147.

4. Regulation for the carriage of dangerous goods on the Rhine(ADNR 2005), Commission Central pour la navigation duRhine, ISBN: 2-912280-33-8.

A P P E N D I X 1

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Classification of three fertilizer compositions is illustrated on threecorresponding logic diagrams below based on the source materialcontent. It is assumed that the organic/combustible material contentis within the specified limits.

Example 1:Fertilizer composition by weight %Ammonium nitrate 75Calcium carbonate or dolomite 21Ammonium sulphate 4

Answer: The fertilizer is not classified. Clearly, the addition ofammonium sulphate is quite small and is to improve quality.The fertilizer can be regarded as a mixture of AN andlimestone (or dolomite).

Example 2:Fertilizer composition by weight %Ammonium nitrate 75Calcium carbonate or dolomite 10Inert e.g. calcium sulphate or gypsum 15

Answer: The fertilizer is classified as an oxidiser, class 5.1. (Incountries where special derogation may be in operation, thisclassification may not apply).

Example 3:Fertilizer composition by weight %Ammonium nitrate 69MOP (KCl) 9Ammonium sulphate 22

Trough test shows it to be not capable of self-sustainingdecomposition.

Answer: The fertilizer is not classified.

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both NO3- and NH4





(Note 2)


Ref SP 306


UN 2067 Class 5.1

Ref. SP 306


(Note 5)





(Note 9)

No

Yes No

Yes

Yes

No

No

No

Figure 2

NoYes

Yes

Yes

Yes

No


(Note 4)

Yes

No


(Note 3)

AN > 70%Ref SP 307 (b)

(Note 2)

Figure 1

Example 1: 75% AN, 21% Dolomite and 4% AS

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(Note 4)

AN > 80%Ref SP 307 (b)

(Note 2)

Not classifiedas

hazardous

Yes


(Note 4)

AN > 45%

AN + AS > 70%?(Note 2)

No

No

UN 2067 Class 5.1

Ref. SP 306

No



AN > 70%?(Note 2)

No

Not classifiedas


(Note 8)

No

AN < 70% See Note 6

Yes

Yes

No

Yes


No

Yes

Yes

No

Yes

UN 2067Class 5.1

Ref. SP 306Yes


(Note 5)

From Figure 1

Figure 2

Example 1: 75% AN, 21% Dolomite and 4% AS

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both NO3- and NH4





(Note 2)


Ref SP 306


UN 2067 Class 5.1

Ref. SP 306


(Note 5)





(Note 9)

No

Yes No

Yes

Yes

No

No

No

Figure 2

NoYes

Yes

Yes

Yes

No


(Note 4)

Yes

No


(Note 3)

AN > 70%Ref SP 307 (b)

(Note 2)

Figure 1

Example 2: 75% AN, 10% Dolomite and 15% Calcium sulphate

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(Note 4)

AN > 80%Ref SP 307 (b)

(Note 2)

Not classifiedas

hazardous

Yes


(Note 4)

AN > 45%

AN + AS > 70%?(Note 2)

No

No

UN 2067 Class 5.1

Ref. SP 306

No



AN > 70%?(Note 2)

No

Not classifiedas


(Note 8)

No

AN < 70% See Note 6

Yes

Yes

No

Yes


No

Yes

Yes

No

Yes

UN 2067Class 5.1

Ref. SP 306Yes


(Note 5)

From Figure 1

Figure 2

Example 2: 75% AN, 10% Dolomite and 15% Calcium sulphate

20



both NO3- and NH4





(Note 2)


Ref SP 306


UN 2067 Class 5.1

Ref. SP 306


(Note 5)





(Note 9)

No

Yes No

Yes

Yes

No

No

No

Figure 2

NoYes

Yes

Yes

Yes

No


(Note 4)

Yes

No


(Note 3)

AN > 70%Ref SP 307 (b)

(Note 2)

Figure 1

Example 3: 69% AN, 9% MOP and 22% AS

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(Note 4)

AN > 80%Ref SP 307 (b)

(Note 2)

Not classifiedas

hazardous

Yes


(Note 4)

AN > 45%

AN + AS > 70%?(Note 2)

No

No

UN 2067 Class 5.1

Ref. SP 306

No



AN > 70%?(Note 2)

No

Not classifiedas


(Note 8)

No

AN < 70% See Note 6

Yes

Yes

No

Yes


No

Yes

Yes

No

Yes

UN 2067Class 5.1

Ref. SP 306Yes


(Note 5)

From Figure 1

Figure 2

Example 3: 69% AN, 9% MOP and 22% AS

A P P E N D I X 2

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Ammonium Nitrate (AN) ContentThe content of ammonium nitrate in a fertilizer is calculated on thebasis of nitrate ions for which a molecular equivalent of ammoniumions is present.

The nitrogen content of AN is 35%. The following table gives thenitrogen content in fertilizers derived from AN on a wt/wt basis.

Example 1:

The ammonium nitrate (AN) content of a fertilizer which contains7% nitrate nitrogen and 12% ammoniacal nitrogen is calculated asfollows:

Nitrogen content derived from ammonium nitrate (formulaNH4NO3)

= 7% nitrate N + 7% ammoniacal N

= 14% N

As pure ammonium nitrate contains 35% nitrogen, the ammoniumnitrate content of this fertilizer is:

1435

x 100 = 40%

Example 2:The ammonium nitrate (AN) content of a fertilizer which is made of60% potassium nitrate (KNO3) and 40% MAP (NH4H2PO4) can becalculated as follows:

Potassium nitrate contains nil ammoniacal N and 13.86% nitrate N.

Pure MAP contains 14/115 x 100 or 12.2% ammoniacal N and nilnitrate-N. (Commercial MAP contains slightly less amounts ofnutrients due to the presence of other substances.)

AN % 100 90 80 70 60 45 30

N % 35 31.5 28 24.5 21 15.75 10.5

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Therefore, the mixture contains:

nitrate-N = 60 x 13.86/100 or 8.3% and ammoniacal-N = 40 x12.2/100 or 4.9%.

The ammoniacal N, being less than the nitrate N, is the limitingnumber. Total N in equivalent AN = 2 x 4.9 or 9.8%.

Therefore, equivalent Ammonium Nitrate = (9.8/35%) or 28%.

N O T E S

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Guidance for UN Classification of Ammonium Nitrate Based Substances (2006)

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