Hazardous materials – Dangerous goods - A complete guide

What are hazardous materials?

Hazardous materials are articles or substances that can pose a significant risk to human health and life, as well as to the environment. By their physical and chemical properties, they have the potential to cause sudden and uncontrollable danger.

In legal terms, on the other hand, hazardous materials are goods the carriage of which is prohibited or permitted only under the conditions set out in the ADR agreement.

Such materials are divided into nine classes, which you will read more about in a moment.

What are examples of hazardous materials?

Examples of hazardous materials are:

• Ammunition, gunpowder, fuses, bombs, cartridges, demolition charges, fuses, flares, mines; 
• Inflammable alcohols; 
• Inflammable aldehydes, liquid tars, pesticides; 
• Liquid nicotine compounds, pneumatic or hydraulic pressure objects, self-heating materials, clinical waste, first aid kits; 
• Cyanides, organometallic compounds, cell liners, iodine, mercury, chemicals under pressure; 
• Flammable inks, other paints (as well as wood stain, stains, varnishes, enamels, etc.); 
• Wood preservatives, xylenes, powdered aluminium, oily fibres or fabrics, unstabilised fish meal; 
• Acids, compressed air, coal gas, adhesives containing flammable liquids, liquid aromatic extracts; 
• Magnesium powder, lithium, zinc, nitrates, persulphates, solid and liquid arsenic compounds, cacodylic acid; 
• Radioactive materials, corrosive and inflammable materials; 
• Alcoholic beverages; 
• Nitroglycerine, nitrourea, gunpowder pulp, missiles, rockets, rocket engines; 
• Fusel oil, engine fuel, gas oil, fuel oil; 
• Paper containing unsaturated oil; 
• Petroleum, resin oil, shale oil, ethanol, medical plasters, turpentine, ether; 
• Disinfectants, dyes, hydrocyanic acid; 
• Candles emitting tear gas, aviation fuel, resin in solution; 
• Signaling devices, sound devices, cartridge primers, alarm signals, warheads, octolite, propelling charges, grenades, fireworks, torpedoes;
• Perfumery products; 
• Matches, lighters.

What are the hazardous material classes?

The classes of hazardous materials are as follows:

• Class 1 - Explosives and Articles with explosives; 
• Class 2 - Gases; 
• Class 3 - Flammable liquids; 
• Class 4 - Three subgroups: 
• Class 4.1 - Flammable solids, self-reactive materials, polymerizable materials, and desensitized solid explosives; 
• Class 4.2 - Materials susceptible to spontaneous ignition; 
• Class 4.3 - Materials producing flammable gases with water; 
• Class 5 - Two subgroups: 
• Class 5.1 - Oxidising materials; 
• Class 5.2 - Organic peroxides; 
• Class 6 - Two subgroups: 
• Class 6.1 - Poisonous materials; 
• Class 6.2 - Infectious materials; 
• Class 7 - Radioactive materials; 
• Class 8 - Corrosive materials; 
• Class 9 - Other hazardous materials and articles.

This gives a total of 13 classes (including 9 main classes) according to the ADR classification.

Class 1 - Explosives and Articles with explosives

Class 1 includes solid and liquid substances that, as a result of a chemical reaction, can emit gases at such a temperature, pressure and speed that they threaten to destroy the environment (e.g. explosives, fireworks, ammunition, etc.).

There is also a distinction here between six subclasses:

• 1.1 - Materials and articles which present a mass explosion hazard; 
• 1.2 - Materials and articles that present a projection hazard; 
• 1.3 - Materials and articles that present a fire hazard and a low explosion or projection hazard, or both, but which do not present a mass explosion hazard; 
• 1.4 - Materials and articles which present only a low explosion hazard if ignited or initiated during carriage; 
• 1.5 - Extremely insensitive materials that present a mass explosion hazard which are so insensitive that they are unlikely to initiate or transition from burning to detonation under normal conditions of carriage; 
• 1.6 - Extremely insensitive items that do not present a mass explosion hazard.

In addition, explosives are divided into 13 compatibility groups (A to S).

Class 2 - Gases

Class 2 includes pure gases, mixtures of gases, mixtures of one or more gases with other objects, and goods containing gases. A common hazard with gases is the risk of a physical explosion (due to high pressure) or a chemical explosion (due to a chemical reaction).

Furthermore, gases are divided into subclasses:

• 2.1 - Flammable gases; 
• 2.2 - Non-flammable and non-poisonous gases;
• 2.3 - Poisonous gases.

Class 3 - Flammable liquids

Class 3 includes liquids and explosive desensitised liquids which have a flash point of not more than 60°C. Also those which, although they have a flash point higher than 60°C, are transported heated to a temperature equal to or higher than their flash point.

Additional hazards of this class may be poisonous, corrosive or both at the same time.

It is also worth mentioning that flammable liquids are classified in their respective packing groups based on their flash point (in a closed crucible) and onset boiling point:

• Packing group I - Boiling point below 35°C; 
• Packing group II - Flash point below 23°C and boiling point above 35°C; 
• Packing group III - Flash point above 23°C and below 60°C, boiling point above 35°C.

Class 4 - Flammable solids, self-reactive materials and those which produce flammable gases when in contact with water

The ADR agreement divides Class 4 into three separate classes:

Class 4.1 - Flammable solids, self-reactive materials and desensitised solid explosives.

Class 4.1 includes:

• Flammable solids - flammable solids that can ignite by friction (e.g. matches); 
• Self-reactive materials - unstable chemicals prone to decomposition by strong exothermic decomposition, even without oxygen (air);
• Desensitised solid explosives - solids moistened with water or alcohol. Also those diluted with other substances that reduce their explosive properties; 
• Polymerising materials - substances which, without stabilisation, are prone to a strong exothermic reaction. 

Class 4.2 - Materials susceptible to self-ignition

Class 4.2 includes:

• Pyrophoric materials - when in contact with air, they ignite spontaneously in no more than 5 minutes; 
• Self-heating materials and objects - in contact with air they are susceptible to self-heating without an external energy supply.

Class 4.3 - Materials which react with water to form flammable gases

Class 4.3 materials react with water as a liquid or vapour to produce a flammable gas. They can also be ignited by the heat of reaction. Therefore, they must be stored in watertight, hermetically sealed containers to avoid the ingress of moisture or steam.

Class 5 - Oxidising materials and organic peroxides

Class 5 is also divided into two separate classes in the ADR agreement:

Class 5.1 - Oxidising materials

Class 5.1 covers materials that are not themselves always flammable, but can ignite or sustain the combustion of another material through the release of oxygen. In addition, it includes items that contain oxidising substances.

Decomposition of Class 5.1 materials (e.g. ammonium nitrate) can lead to explosions. Moreover, the predominant and ancillary (corrosive) hazards make their carriage very dangerous.

Class 5.2 - Organic peroxides

Class 5.2 materials belong to the peroxide group, which is chemically unstable, and are divided into:

• Organic peroxides not requiring temperature control;
• Organic peroxides requiring temperature control.

These types of substances are susceptible to exothermic decomposition, which can be initiated by heat, contact with contaminants e.g. (acids), friction, or impact. The decomposition may give off noxious or flammable gases or vapours and molecular oxygen. Chemical hoses will allow you to safely transport peroxides, e.g. acids, from one point to another.

Class 6 - Toxic and infectious materials

In this case, the ADR agreement also divides Class 6 into two separate classes:

Class 6.1 - Poisonous materials

Class 6.1 covers chemical poisons that are capable of damaging the human body in whole or in part. Therefore, contact with the substance through ingestion, inhalation or absorption through the skin must not be allowed.

Poisonous materials present hazards of varying potency from those that kill within minutes (e.g. cyanides) to those that are harmful but not necessarily lethal at low dose (e.g. chlorinated hydrocarbons). Substances in class 6.1 can be in solid or liquid form.

Toxic gases are found in class 2.3.

Generally, subclass 6.1 materials should not be transported with foodstuffs, but there are exceptions to this rule.

Class 6.2 - Infectious materials

Class 6.2 materials contain pathogens, i.e. micro-organisms that cause infectious diseases in humans or animals. They are divided in terms of hazard into two categories:

• Category A: Includes infectious materials that can cause permanent impairment, life-threatening or fatal disease in previously healthy humans or animals; 
• UN 2814 is assigned to pathogens dangerous to humans and animals;
• UN 2900 is assigned to pathogens dangerous only to animals. 
• Category B: Applies to materials that do not qualify for Category A. They shall be labelled with UN 3373.

Class 7 - Radioactive materials

Class 7 covers materials containing radioactive isotopes in which both the radioactive concentration and the total activity of the consignment exceed the values specified in the ADR (e.g. fissile material or surface contaminated objects).

The classification rules here are different from all other classes. The predominant hazard (radiation emission) is related to the form of the radioactive material, its quantity and the way it is packaged.

Class 8 - Corrosive materials

Goods in class 8 damage living tissue or have a corrosive effect on other materials or means of transport. Also included are substances that form a corrosive liquid only in the presence of water or give off corrosive vapours or mists in conditions of natural moisture in the air.

As an additional hazard, there may be poisonous or oxidising effects, ignitability of liquid or solid material or the danger of emission of flammable gases on contact with water.

Class 9 - Other hazardous materials and articles

Class 9 covers materials and objects that present hazards during transport that do not qualify for the other classes. It also includes goods that present several separate hazards that cross two or more class boundaries.

Examples of Class 9 materials are asbestos, seat belt pretensioners, or airbags.

What are the rules for handling hazardous materials?

The most important rules for handling hazardous materials are as follows:

• Proper storage of hazardous materials - Hazardous substances should be stored in locations and containers designated for that purpose (and appropriately labelled). Packaging must be made of suitable material and have the durability to withstand hazards with its contents. 
• Neutralisers and sorbents - Access to neutralisers and sorbents should be provided in areas where hazardous materials are stored and used. This will make it easier to control spills and prevent their spread.
• Training - Everyone who handles hazardous materials should receive adequate training in how to deal with them. This includes understanding potential hazards, how to properly store and handle substances and how to deal with emergencies. 
• Personal protective equipment - Appropriate personal protective equipment should be worn when handling hazardous materials. This may include gloves, goggles, respirators, and other protective equipment (depending on the substance). 
• Emergency response plan - An emergency response plan for spills or other accidents involving hazardous materials should be implemented. This should include procedures for containment and clean-up of spills, as well as evacuation of the area (if necessary). 
• Disposal - Hazardous materials should be properly disposed of following local regulations. This may include recycling, treating, or disposal in a hazardous waste dump. 
• Documentation - Appropriate documentation should be kept for all hazardous materials on their properties, storage, and disposal. This information should be easily accessible to everyone who handles the materials. 
• Inspection and maintenance - Storage areas and containers for hazardous materials should be inspected regularly to ensure that they are in good condition and free from leaks or other hazards.

What are the certifications and training for hazardous materials?

Certifications and training for hazardous materials are as follows:

• ADR course for drivers, which concludes with an exam and obtaining a certificate authorising the transport of hazardous materials in Poland and abroad. 
• ADR adviser course, which also leads to an exam and certification to work as an ADR adviser. 
• ADR on-the-job training for all those who work with hazardous materials. 
• NO TDT tanker training for those who work in the filling and emptying of tankers. Ends with an exam and the relevant qualifications. 
• Hazardous goods storage training.

How should hazardous materials be packed?

Hazardous materials should be packed in strong and good quality ADR packaging to withstand shocks during transport. Furthermore, they should be sealed in such a way that the contents are not damaged by vibration, pressure, humidity or temperature changes.

Importantly, the packaging must not be made of materials that form hazardous compounds or become damaged on contact with the contents. In addition, there must be no residues of the transported substance on the outer walls.

Last but not least, the package must be properly labelled in accordance with ADR requirements.

What are the markings of hazardous materials?

The markings of hazardous materials are as follows:

• ADR sticker - Contains a pictogram, i.e. a graphic symbol of hazard. Each class has its own symbol (some even several, e.g. one for each subclass); 
• UN number - A four-digit code that refers to a specific substance (e.g. petrol); 
• ADR plate - A marking mounted on vehicles transporting dangerous substances. By means of the HIN and UN number, it indicates what goods are currently being transported.

How to transport hazardous materials?

Hazardous materials must be transported in accordance with all regulations, i.e.:

• The goods must be properly packed and labelled; 
• The vehicle should pass a periodic inspection; ● The transport crew needs the appropriate authorisations; 
• The vehicle must not lack the necessary documents concerning the goods; 
• The vehicle must be properly marked; 
• Each crew member should have their own set of protective equipment.

It is also worth mentioning here that chemical hoses, compatible with the hazardous substance in question, are used to fill the tankers.

What are the regulations of hazardous materials?

The regulation of hazardous materials depends on several factors. First of all, each transport type has its own regulations that apply to this sector of logistics. In addition, there are also separate regulations for the storage and use of hazardous materials in buildings.

Admittedly, there will be overlap in most cases, but it is worth knowing that there are some differences.

What are the regulations of hazardous materials in transport?

The regulation of hazardous materials in transport is as follows:

• Regulations for the International Carriage of Dangerous Goods by Rail (RID);
• International Regulations for the Maritime Transport of Dangerous Goods (IMGD); 
• Technical Safety Instructions for the Transport of Hazardous Materials by Air (ICAO); 
• European Agreement concerning the International Carriage of Dangerous Goods by Inland Waterways (ADN); 
• European Convention on the carriage of dangerous goods and loads by road (ADR).

What are UN numbers for hazardous materials?

UN numbers for hazardous materials are identification numbers. They consist of four digits and are detailed designations of the substance concerned.

For example: the identification number for petrol is UN 1203.

The UN codes were established by the Central Committee of the United Nations. They are intended to make it easier to identify a hazardous material and for the emergency services to respond appropriately.

What are the regulations of hazardous materials in air transport?

The regulation of hazardous materials in air transport is enforced by organisations such as:

• International Air Transport Association (IATA); 
• International Civil Aviation Organisation (ICAO).

The legislation addresses the classification of hazardous goods, their packaging, necessary documentation, training, inspections, etc.

What are the regulations of hazardous materials in road transport?

The regulation of hazardous materials in road transport is set out in the ADR agreement. This is an extensive legal act that contains provisions on the classification of materials, conditions of carriage or the obligations of transport participants.

What are the regulations of hazardous materials in maritime transport?

The regulation of hazardous materials in maritime transport is set out in the International Maritime Dangerous Goods Code (IMDG). In it you will find requirements for packaging, marking, labelling, documentation and procedures related to the transport of hazardous materials.

What is the regulation of hazardous materials in rail transport?

The regulation of hazardous materials in rail transport is set out in the Regulations for the International Carriage of Dangerous Goods by Rail (RID). It contains, inter alia, a list of hazardous goods that can be transported by rail and the requirements for transport and rolling stock.

The second document in force in the Republic of Poland regulating international transport of dangerous goods by rail is Annex 2 to the SMGS Agreement - Regulations on the carriage of hazardous goods.

What are the regulations of hazardous materials for transport on inland waterways?

The regulation of hazardous materials for transport on inland waterways is set out in the European Agreement concerning the International Carriage of Dangerous Goods by Inland Waterways (ADN). This document specifies, among other things:

• Methods of classifying hazardous goods;
• The necessary markings and documentation; 
• Fire-fighting equipment; 
• Vessel equipment; 
• Methods of cargo handling (including dry cargo vessels and tankers);
• Training of crew and persons involved in the carriage of goods;
• Procedures for issuing certificates of release.

What is the regulation of hazardous materials in buildings?

The regulation of hazardous materials in buildings is not uniform, as there is no single law across Europe that sets out the regulations and requirements in this sector. Therefore, the basis for the correct storage of hazardous materials is based on national legislation.

The main regulations of hazardous materials in buildings in the UK are:

• Control of Major Accident Hazards Regulations 1999 (COMAH);
• Chemicals (Hazard Information and Packaging for Supply) Regulations 2002 (CHIP); 
• Control of Substances Hazardous to Health Regulations 2002 (COSHH).

From the above regulations, we conclude that:

• Hazardous materials should be stored in places and packaging intended for this purpose and properly labeled; 
• The premises, apparatus and packaging should be resistant to the properties of the hazardous substances in question; 
• Instructions on how to store, pack, load and transport hazardous materials should be posted in the building. In addition, employees should familiarize themselves with them; 
• The amount of hazardous material at the workplace should not exceed the daily requirement (there are exceptions to this rule); 
• Hazardous goods should be stored so as to minimize the risk of fire or explosion; 
• Hazardous substances that interact with each other should not be stored in one place; 
• All employees should receive training in working with hazardous materials.

In some cases, suitable conditions in buildings and premises are provided by industrial chillers.

What are the safety rules for hazardous material spills?

The safety rules for hazardous material spills are as follows:

• Brake the vehicle, turn off the engine, and disconnect the battery using the main switch (if there is access to it); 
• Brake the vehicle, turn off the engine, and disconnect the battery using the main switch (if there is access to it); 
• Notify the relevant emergency services, providing them with all available information regarding the accident or hazard;
• Wear a warning vest and place standing warning signs accordingly;
• Provide arriving rescue workers with easy access to transport documents; 
• Do not walk on the released materials, do not touch them, avoid inhaling fumes, smoke, dust, and vapors by staying on the windward side;
• Wear acid-resistant goggles, suitable gloves, and boots when handling corrosive materials; 
• Use extreme caution when spilling poisonous materials, even though using a mask. Do not seal the spill. The mask has an escape function only; 
• If appropriate and safe, use fire extinguishers to extinguish a small or incipient fire (e.g., tires, brakes or engine compartment);
• Vehicle crew members should not extinguish a fire involving the cargo compartment;
• As far as possible and safe, prevent released substances from entering the water environment or sewerage system (e.g., by using sand). In the case of solids, collect the released materials with the equipment carried in the transport unit; 
• Move away from the site of the accident or hazard. In addition, inform others to move away and follow the recommendations of the emergency services;
• Remove and dispose of contaminated clothing and used, contaminated protective equipment in a safe manner.

What are dangerous goods?

Dangerous goods are substances and objects that can endanger the health and life of people and the environment as a result of improper storage and transport.

What are ADR hazardous materials?

ADR hazardous materials are materials and articles the carriage of which is prohibited or authorised only under the conditions set out in the ADR Agreement. The full list of hazardous goods (both authorised and non-authorised) can be found in Table A of the ADR Agreement. Each item corresponds to a four-digit number, called the UN number, as well as the name and description of the hazardous goods concerned.

Who classifies hazardous goods?

Hazardous goods are classified by the manufacturer or shipper. They can carry out the classification procedure themselves - provided they have the necessary facilities or laboratory support to carry out the tests as prescribed by the regulations.

The final phase, i.e. the interpretation of the results contained in the test report, usually involves the dangerous goods transport safety advisor.

Is coal a hazardous good?

Coal is a hazardous commodity that is classified1 as Class 4.2, materials prone to self-ignition. However, hard coal, coke and anthracite qualify for Packing Group III (as a low-hazard good) and are not subject to ADR regulations for road transport. The RIG regulations for railways are more stringent.

Which hazardous goods are classified as high risk goods?

Hazardous goods that can be misused (e.g. in terrorist attacks), resulting in casualties or massive destruction of the environment or infrastructure are classified as high risk goods.

This group includes high-activity radioactive materials, explosives or poisonous substances. In addition, some materials from other classes will also be high-risk goods if they are transported in large quantities.

What are the most common types of hazardous materials?

The most common types of hazardous materials are petrol and diesel, chlorine, firecrackers and dynamite, matches and magnesium, as well as battery acid and solvent.

Is oil a hazardous material?

Yes, oil is a hazardous material. It is classified as a Class 3, flammable liquid.

How to identify hazardous materials?

To identify hazardous materials, you can use the dangerous goods classifications available in the ADR agreement.

Is glass a hazardous material?

Glass is not a hazardous material unless it is contaminated with some harmful substance.

Summary

In this article, we explained what hazardous materials are and their classification. In addition, we have checked the rules for handling them during transport and storage against current legislation.

The above information will help you to better understand this industry sector. Especially when it comes to a safe and regulated approach to transporting and storing substances that are hazardous to humans and the environment.