9.2 Hazard classification

9.2.1 The classification of materials possessing chemical hazards and intended to be shipped in bulk under the requirements of this Code shall be in accordance with 9.2.2 and 9.2.3.

9.2.2 Classification of dangerous goods

SOLAS regulation VII/7 defines dangerous goods in solid form in bulk. For the purpose of this Code, dangerous goods shall be classified in accordance with part 2 of the IMDG Code.

9.2.2.1 Class 4.1: Flammable solids

The materials in this class are readily combustible solids and solids which may cause fire through friction.

9.2.2.2 Class 4.2: Substances liable to spontaneous combustion

The materials in this class are materials, other than pyrophoric materials, which, in contact with air without energy supply, are liable to self-heating.

9.2.2.3 Class 4.3: Substances which, in contact with water, emit flammable gases

The materials in this class are solids which, by interaction with water, are liable to become spontaneously flammable or to give off flammable gases in dangerous quantities.

9.2.2.4 Class 5.1: Oxidizing substances

The materials in this class are materials that, while in themselves not necessarily combustible, may, generally by yielding oxygen, cause, or contribute to, the combustion of other material.

9.2.2.5 Class 6.1: Toxic substances

The materials in this class are materials liable either to cause death or serious injury or to harm human health if swallowed or inhaled, or by skin contact.

9.2.2.6 Class 7: Radioactive material

The materials in this class are any materials containing radionuclides where both the activity concentration and the total activity in the consignment exceed the values specified in 2.7.2.2.1 to 2.7.2.2.6 of the IMDG Code.

9.2.2.7 Class 8: Corrosive substances

The materials in this class are materials which, by chemical action, will cause severe damage when in contact with living tissue or will materially damage, or even destroy, other goods or the means of transport.

9.2.2.8 Class 9: Miscellaneous dangerous substances and articles

The materials in this class are materials and articles which, during transport, present a danger not covered by other classes.

9.2.3 Materials hazardous only in bulk (MHB)

9.2.3.1 General

9.2.3.1.1 These are materials which, when carried in bulk, possess chemical hazards other than the hazards covered by the classification system of the IMDG Code. These materials present a significant risk when carried in bulk and require special precautions.

9.2.3.1.2 A material shall be classified as MHB if the material possesses one or more of the chemical hazards (excluding those hazards which are covered by the classification system of the IMDG Code) as defined below. When a test method is prescribed, representative samples of the cargo to be carried shall be used for testing. Samples shall be taken 200 to 360 mm inward from the surface at 3 m intervals over the length of a stockpile.

9.2.3.1.3 A material may also be classified as MHB by analogy with similar cargoes with known hazardous properties or by records of accidents.

9.2.3.1.4 Although the chemical hazards are intended to be closely defined in order to establish a uniform approach to MHB classification, where human experience or other factors indicate the need to consider other chemical hazards, these shall always be taken into account. Where deviations from the chemical hazards described in 9.2.3.2 to 9.2.3.7 have been recognized (Other hazards (OH)), they shall be properly recorded with justifications. Other hazards are to be included in the section for "Hazard" in the individual schedule.

9.2.3.1.5 A notational reference shall be provided in the "MHB" cell of the Characteristics table for each individual schedule for cargoes classified as MHB. When a material possesses one or more of the chemical hazards as defined below, the notational reference for each hazard shall be included in the "MHB" cell. A summary of the notational references is presented in the table below:

9.2.3.2 Combustible solids: MHB (CB)

9.2.3.2.1 These are materials which are readily combustible or easily ignitable when transported in bulk and do not meet the established criteria for inclusion in class 4.1 (see 9.2.2.1 of this Code).

9.2.3.2.2 Powdered, granular or pasty materials shall be classified as MHB when the time of burning of one or more of the test runs, performed in accordance with the preliminary screening test method described in the United Nations Manual of Tests and Criteria, part III, 33.2.1.4.3.1, is less than 2 min. Powders of metals or metal alloys shall be classified as MHB when they can be ignited and the reaction spreads over the whole length of the sample in 20 min or less. The test sample in the preliminary screening test is 200 mm in length. A summary of this approach is presented in the table below:

9.2.3.3 Self-heating solids: MHB (SH)

9.2.3.3.1 These are materials that self-heat when transported in bulk and do not meet the established criteria for inclusion in class 4.2 (see 9.2.2.2).

9.2.3.3.2 A material shall be classified as MHB if, in the tests performed in accordance with the test method given in the United Nations Manual of Tests and Criteria, part III, 33.3.1.6, the temperature of the test sample rises by more than 10°C when using a 100 mm cube sample at 140°C and at 100°C. The following flow chart illustrates the test procedure.

9.2.3.3.3 In addition, a material shall be classified as MHB if a temperature rise of 10°C or more over ambient temperature is observed during any portion of the test performed in accordance with the test method described in United Nations Manual of Tests and Criteria, part III, 33.4.1.4.3.5. When performing this test, the temperature of the sample should be measured continuously over 48 hours. If, at the end of the 48-hour period the temperature is increasing, the test period shall be extended in accordance with the test method.

9.2.3.4 Solids that evolve flammable gas when wet: MHB (WF)

9.2.3.4.1 These are materials that evolve flammable gases when in contact with water when transported in bulk and do not meet established criteria for inclusion in class 4.3 (see 9.2.2.3).

9.2.3.4.2 A material shall be classified as MHB if, in tests performed in accordance with the test method given in the United Nations Manual of Tests and Criteria, part III, 33.4.1, the flammable gas evolution rate is greater than zero. When performing this test, the rate of evolution of gas shall be calculated over 48 hours at one-hour intervals. If at the end of the 48-hour period the rate of evolution is increasing, the test period shall be extended in accordance with the test method.

9.2.3.5 Solids that evolve toxic gas when wet: MHB (WT)

9.2.3.5.1 These are materials that evolve toxic gases when in contact with water when transported in bulk.

9.2.3.5.2 A material shall be classified as MHB if, in tests performed in accordance with the test method given in the United Nations Manual of Tests and Criteria, part III, 33.4.1, the toxic gas evolution rate is greater than zero. Toxic gas evolution shall be measured using the same test procedure for flammable gas evolution as prescribed in the test method. When performing this test, the rate of evolution of gas shall be calculated over 48 hours at 1-hour intervals. If at the end of the 48-hour period the rate of evolution is increasing, the test period shall be extended in accordance with the test method.

9.2.3.5.3 The gas shall be collected over the test period prescribed above. The gas shall be chemically analysed and tested for toxicity if the gas is unknown and no acute inhalation toxicity data is available. If the gas is known, inhalation toxicity shall be assessed based on all information available, using testing as a last resort option for concluding this hazard. Toxic gases in this respect are gases showing acute inhalation toxicity (LC₅₀) of or below 20,000 ppmV or 20 mg/L by 4 hours' testing (GHS Acute Toxicity Gases/Vapours Category 4).

9.2.3.6 Toxic solids: MHB (TX)

9.2.3.6.1 These are materials that have toxic hazards to humans if inhaled or with contact with skin when loaded, unloaded, or transported in bulk and do not meet the established criteria for inclusion in class 6.1 (see 9.2.2.5).

9.2.3.6.2 A material shall be classified as MHB in accordance with the criteria laid down within part 3 of the GHS:

• .1 cargoes developing cargo dust with an acute inhalation toxicity (LC₅₀) of 1-5 mg/L by 4 hours' testing (GHS Acute Toxicity Dusts Category 4);

• .2 cargoes developing cargo dust exhibiting an inhalation toxicity of equal to or less than 1 mg/L/4 h (GHS Specific Target Organ Toxicity Single Exposure Inhalation Dust Category 1) or below 0.02 mg/L/6 h/d (GHS Specific Target Organ Toxicity Repeated Dose Inhalation Dust Category 1);

• .3 cargoes exhibiting an acute dermal toxicity (LD₅₀) of 1,000-2,000 mg/kg (GHS Acute Toxicity Dermal Category 4);

• .4 cargoes exhibiting a dermal toxicity of or below 1,000 mg (GHS Specific Target Organ Toxicity Single Exposure Dermal Category 1) or below 20 mg/kg bw/d by 90 days' testing (GHS Specific Target Organ Toxicity Repeated Dose Dermal Category 1);

• .5 cargoes exhibiting carcinogenicity (GHS Category 1A and 1B), mutagenicity (GHS Category 1A and 1B) or reprotoxicity (GHS Category 1A and 1B).

9.2.3.7 Corrosive solids: MHB (CR)

9.2.3.7.1 These are materials that are corrosive to skin, eye or to metal or are respiratory sensitizers and do not meet the established criteria for inclusion in class 8 (see 9.2.2.7).

9.2.3.7.2 A material shall be classified as MHB in accordance with the criteria laid down within part 3 of the GHS:

• .1 cargoes which are known to be a respiratory sensitizer (GHS Respiratory Sensitization Category 1);

• .2 cargoes exhibiting skin irritation with a mean value of or higher than 2.3 for erythema/eschar or oedema (GHS Skin Corrosion/Irritation Category 2);

• .3 cargoes exhibiting eye irritation with a mean value of or higher than 1 for corneal opacity/irititis or 2 for conjunctival redness/oedema (GHS Serious Eye Damage Category 1 or Eye Irritation Category 2A).

9.2.3.7.3 A material shall be classified as MHB when the corrosion rate on either steel or aluminium surfaces is between 4 mm and 6.25 mm a year at a test temperature of 55°C when tested on both materials. For the purposes of testing steel, type S235JR+CR (1.0037 resp. St 37-2), S275J2G3+CR (1.0144 resp. St 44-3), ISO 3574:1999, Unified Numbering System (UNS) G10200 or SAE 1020, and for testing aluminium, non-clad, types 7075-T6 or AZ5GU T6 shall be used. An acceptable test is prescribed in the United Nations Manual of Tests and Criteria, part III, section 37. When this test is performed the sample shall contain at least 10% moisture by mass. If the representative sample of the cargo to be shipped does not contain more than 10% moisture by mass, water shall be added to the sample.