A UN number, also known as a United Nations number, is a four-digit code assigned to hazardous substances, materials, and articles to uniquely identify them for safe transportation purposes across international borders by road, rail, sea, and air.[1] These numbers, ranging from 0004 to approximately 3600, are integral to global regulations on dangerous goods, enabling consistent classification, packaging, labeling, and emergency response protocols to minimize risks during transit.The UN number system originates from the United Nations Model Regulations on the Transport of Dangerous Goods, first published in 1956 by the UN Economic and Social Council's Committee of Experts, and maintained by the United Nations Economic Commission for Europe (UNECE).[2] These model regulations serve as the foundation for international agreements such as the European Agreement concerning the International Carriage of Dangerous Goods by Road (ADR), the International Maritime Dangerous Goods Code (IMDG), and the International Air Transport Association (IATA) Dangerous Goods Regulations, ensuring harmonized standards worldwide.[3] Each UN number corresponds to an entry in the official Dangerous Goods List, which includes the proper shipping name, hazard class, packing group, and special provisions for handling the material.[4]Dangerous goods are categorized into nine hazard classes under the UN system: Class 1 (explosives), Class 2 (gases), Class 3 (flammable liquids), Class 4 (flammable solids, self-reactive substances, and solid desensitized explosives), Class 5 (oxidizing substances and organic peroxides), Class 6 (toxic and infectious substances), Class 7 (radioactive material), Class 8 (corrosive substances), and Class 9 (miscellaneous dangerous substances and articles).[5] This classification helps determine the appropriate transport conditions, such as segregation, quantity limits, and protective equipment, while UN numbers must appear on shipping documents, packages, and placards to facilitate rapid identification by carriers, inspectors, and first responders.[6] The system's ongoing revisions, with the 24th revised edition released in 2025 and including new provisions for battery-powered vehicles and sodium-ion batteries, incorporate scientific advancements and incident lessons to enhance safety amid increasing global trade volumes.[7]
Definition and Purpose
Definition
A UN number is a four-digit numerical code assigned to hazardous substances, materials, and articles to facilitate their identification during international transport by various modes, including road, rail, sea, and air.[8] These codes are developed and maintained by the United Nations Committee of Experts on the Transport of Dangerous Goods to promote uniformity and safety in global commerce.[9]For example, UN 1203 identifies gasoline, a flammable liquid; UN 1845 designates dry ice (carbon dioxide, solid); and UN 2074 specifies acrylamide, a toxic substance.[10] The UN number functions as a concise, standardized identifier, separate from the proper shipping name, which offers a more descriptive label for the material to aid in handling and regulatory compliance.[11]
Purpose in Hazardous Materials Transport
UN numbers serve as a standardized four-digit identificationsystem for hazardous materials, enabling uniform recognition and handling across global transport modes to prevent accidents and ensure safety. By providing a consistent reference for dangerous goods, these numbers facilitate international harmonization, reducing miscommunication and errors during shipping that could lead to spills, fires, or explosions. This uniformity is essential for regulatory compliance, as it aligns with the United Nations Recommendations on the Transport of Dangerous Goods, which form the basis for modal regulations worldwide.[9]In practice, UN numbers are mandatory on shipping documents, such as dangerous goods declarations, as well as on placards and packaging labels to clearly indicate the contents and associated risks. Under the International Maritime Dangerous Goods (IMDG) Code, for instance, they must appear on cargo transport units and documentation to specify the exact substance, supporting safe stowage and segregation on vessels. Similarly, the International Air Transport Association (IATA) Dangerous Goods Regulations require UN numbers on air waybills and packages to comply with aviation safety standards, streamlining customs clearance and inspections. These requirements ensure that carriers, handlers, and authorities can quickly verify compliance without ambiguity.[12][13]UN numbers support the classification of hazardous materials into nine distinct classes—such as Class 1 for explosives or Class 3 for flammable liquids—while deliberately not encoding the class within the number itself to maintain neutrality and focus on unique substance identification. This separation allows for flexible application across transport modes and prevents premature assumptions about risks, with full hazard details accessed via accompanying proper shipping names and labels. The system promotes efficient regulatory oversight by linking directly to safety protocols in the UN Model Regulations.[14]For first responders, UN numbers provide critical benefits by enabling rapid access to essential information during incidents, such as through the U.S. Department of Transportation's Emergency Response Guidebook (ERG). By referencing the four-digit code on placards or documents, responders can consult the ERG's indexed tables to identify initial actions, protective distances, and evacuation guidelines, minimizing exposure and optimizing response times. This quick-lookup mechanism has proven vital in real-world emergencies, enhancing overall transport safety.[15]
History and Development
Origins in International Agreements
The development of UN numbers originated in the 1950s as part of United Nations initiatives aimed at standardizing the international transport of dangerous goods, driven by the post-World War II imperative to rebuild global trade infrastructure and prevent accidents during cross-border shipments.[16] Following the war's devastation of transport networks, the UN Economic Commission for Europe (UNECE) and its Inland Transport Committee prioritized harmonized regulations to facilitate safe and efficient movement of hazardous materials, addressing inconsistencies in national rules that had previously hindered economic recovery.[16]The foundational work began with the establishment of an ad hoc Committee of Experts on the Transport of Dangerous Goods by the UN Economic and Social Council (ECOSOC) in 1953, tasked with developing uniform recommendations for classifying and handling dangerous substances.[17] This committee's efforts culminated in the first edition of the UN Recommendations on the Transport of Dangerous Goods, published in 1956, which introduced a systematic numbering scheme—later known as UN numbers—for identifying hazardous materials and outlined basic provisions for their safe carriage.[18]In 1957, ECOSOC formalized the committee as a permanent body, the Committee of Experts on the Transport of Dangerous Goods, with a mandate to periodically update the recommendations and expand their scope.[19] Initially, the focus was on rail and road transport to align with emerging European agreements like the 1957 Convention on the International Carriage of Dangerous Goods by Road (ADR), reflecting the era's emphasis on land-based recovery logistics.[20] By the 1960s, the recommendations evolved to encompass multimodal transport, incorporating sea, air, and inland waterways to support growing global commerce.[21] This progression laid the groundwork for the modern "Orange Book," the informal name for the ongoing revisions of these model regulations.[8]
Evolution and Key Milestones
The UN Recommendations on the Transport of Dangerous Goods, commonly known as the Orange Book, were first published in 1956, establishing the foundational framework for the UN numbering system to classify and identify hazardous materials internationally.[8] In the 1970s, the system underwent significant integration as the Recommendations were revised periodically to incorporate feedback from global transport experts, enhancing consistency across modes of transportation and laying the groundwork for broader adoption.[21] These revisions emphasized the assignment of four-digit UN numbers by the United Nations Committee of Experts on the Transport of Dangerous Goods, ensuring a standardized identification process.During the 1980s and 1990s, the UN numbering system achieved key harmonization with modal regulations, particularly for air and sea transport. The International Civil Aviation Organization (ICAO) incorporated the UN system into its Technical Instructions for the Safe Transport of Dangerous Goods by Air in 1984, while the International Air Transport Association (IATA) aligned its Dangerous Goods Regulations accordingly to facilitate global air shipments. Similarly, the International Maritime Organization (IMO) harmonized the International Maritime Dangerous Goods (IMDG) Code with the UN Recommendations starting in the 1981 edition, promoting uniformity in maritime transport and reducing discrepancies in hazard identification worldwide.In the 2000s, the system expanded to address emerging risks, including environmental hazards and lithium batteries. New UN numbers, such as UN 3077 for environmentally hazardous substances, solid, n.o.s., and UN 3082 for environmentally hazardous substances, liquid, n.o.s., were refined and more widely applied to cover marine pollutants and other ecological threats, reflecting heightened global environmental concerns. Post-2009 revisions introduced specific UN numbers for lithium batteries, including UN 3480 for lithium ion batteries and UN 3090 for lithium metal batteries, in response to incidents highlighting their thermal runaway risks during transport.A pivotal milestone occurred with the 21st revised edition of the Recommendations in 2019, which introduced UN 3549 for Category A infectious substances from medical or veterinary treatment, and refined entries for UN 2814, UN 2900, and UN 3291, improving classification for clinical waste and biological materials amid growing biosafety needs.[22]The Orange Book continues to evolve through biennial revisions, incorporating amendments from the UN Committee of Experts to adapt to technological advances and safety data. Subsequent biennial revisions continued this trend, with the 22nd edition in 2021, 23rd in 2023, and 24th in 2025 introducing updates such as new UN numbers for sodium-ion batteries (UN 3551–3556) and provisions to support decarbonization in dangerous goods transport, reflecting ongoing adaptations to emerging technologies and environmental priorities.[7]
Numbering System
Structure and Format
A UN number is a four-digit identification code prefixed by the letters "UN" to uniquely identify hazardous substances, materials, or articles for transport purposes. For numbers less than 1000, leading zeros are used to maintain the four-digit format, such as UN 0004 for ammonium picrate, dry or wetted with less than 10% water, by mass.[23]The digits in a UN number do not carry inherent meaning related to the type of hazard or substance properties; instead, they serve as arbitrary serial identifiers assigned by the United Nations Committee of Experts on the Transport of Dangerous Goods.[24] This system ensures consistent global recognition without implying sequential ordering by hazard class or risk level.[25]In practice, UN numbers are displayed on vehicles, containers, or packages using standardized conventions, such as black lettering on orange panels or placards for bulk quantities of dangerous goods, facilitating rapid identification during transport and emergencies.[26] Each UN number directly corresponds to an entry in the Dangerous Goods List of the UN Model Regulations, where it is paired with the associated proper shipping name, hazard classification, and packing instructions to guide safe handling.[27]
Range and Assignment Process
The range of UN numbers provides a structured framework for identifying hazardous substances and articles in international transport, beginning at UN 0004 and extending to UN 3560 as of the 24th revised edition (2025).[7] This span includes over 3,500 active numbers, with deliberate gaps incorporated to accommodate future assignments and ensure long-term scalability of the system. The 2025 revision added 10 new numbers (UN 3551 to UN 3560), including entries for sodium-ion batteries (e.g., UN 3551) and fire suppressant dispersing devices (UN 3559), reflecting advancements in technology and safety needs.[7]Assignment authority resides with the United Nations Sub-Committee of Experts on the Transport of Dangerous Goods, a body under the Economic and Social Council's Committee of Experts, which evaluates and allocates numbers based on formal proposals submitted by member states, international organizations, or industry stakeholders.[14][28] The core criteria require each number to serve as a unique identifier for a specific substance or article, supported by detailed submissions encompassing physical and chemical properties, hazard profiles, and proposed transport conditions to maintain global consistency and safety.[29]The evaluation process involves scrutiny of safety data, hazard classification alignment with UN criteria, and development of packing instructions during the Sub-Committee's biannual sessions, where proposals are debated and refined. Successful assignments are integrated into the biennial updates of the UN Recommendations on the Transport of Dangerous Goods, Model Regulations (Orange Book), ensuring periodic review and adaptation. For novel substances undergoing testing or limited initial transport, provisional numbers may be granted to facilitate safe movement while full classification is finalized.[30][8]
Hazard Identification
Associated Hazard Classes
The United Nations system for the transport of dangerous goods classifies substances and articles into nine primary hazard classes based on their inherent properties and potential risks during transportation. This classification ensures standardized identification and handling protocols globally, as outlined in the UN Recommendations on the Transport of Dangerous Goods, Model Regulations.[30] The classes are defined as follows:
Gases: Compressed, liquefied, or dissolved gases under pressure that present hazards due to flammability, toxicity, or other properties; subdivided into 2.1 (flammable), 2.2 (non-flammable, non-toxic), and 2.3 (toxic).
3
Flammable liquids: Liquids with a flash point of not more than 60°C, or any liquid mixture containing one or more flammable components.
4
Flammable solids, substances liable to spontaneous combustion, or substances emitting flammable gases on contact with water: Includes self-reactive substances and desensitized explosives; subdivided into 4.1 (flammable solids), 4.2 (spontaneous combustion), and 4.3 (water-reactive).
5
Oxidizing substances and organic peroxides: Materials that may cause or enhance combustion, or decompose exothermically; subdivided into 5.1 (oxidizing) and 5.2 (organic peroxides).
6
Toxic and infectious substances: Materials that can cause death, injury, or harm through chemical action or infection; subdivided into 6.1 (toxic) and 6.2 (infectious).
7
Radioactive material: Substances emitting ionizing radiation that pose risks to health and the environment.
8
Corrosive substances: Materials that can cause severe damage to living tissue or corrode metals.
9
Miscellaneous dangerous substances and articles: Substances or articles presenting hazards not covered by other classes, such as environmentally hazardous materials or genetically modified organisms.
Each UN number corresponds to a specific dangerous good or group of goods and is assigned to one primary hazardclass in the UN Model Regulations' Dangerous Goods List (as of the 24th revised edition, 2025), which provides detailed classification information for over 3,000 entries. For instance, UN 1090 for acetone is classified under Class 3 as a flammable liquid due to its low flash point and volatility.[31] The structure of the UN number itself—typically a four-digit code from 0004 to 3558 (as of the 23rd revised edition, 2023)—does not indicate the hazard class, requiring direct reference to the official Dangerous Goods List for accurate identification.[30]Certain classes include further divisions to specify the degree and type of hazard, allowing for more precise risk assessment and packaging requirements. Class 1 (Explosives), for example, is subdivided into six divisions based on the nature and extent of the explosive effect: Division 1.1 covers substances presenting a mass explosion hazard, where nearly all material detonates simultaneously, posing the greatest risk; in contrast, Division 1.4 includes articles presenting only a minor explosion hazard or projection hazard with limited fire potential.[32] These subdivisions ensure that transport conditions reflect the specific dangers, such as prohibiting air shipment for high-risk 1.1 materials while permitting limited quantities of 1.4 items. While the primary class defines the core hazard, some entries may note subsidiary risks from other classes, influencing additional labeling but not altering the primary assignment.[30]
Subsidiary Risks and Labeling
Subsidiary risks refer to secondary hazards posed by a dangerous good in addition to its primary hazard class, as defined in the UN Model Regulations on the Transport of Dangerous Goods. These risks are identified in the dangerous goods list by listing additional class or division numbers following the primary classification. For instance, UN 2927, toxic liquid, corrosive, organic, n.o.s., has a primary class of 6.1 (toxic substances) with a subsidiary risk of class 8 (corrosive substances).[33] In cases where a material exhibits multiple secondary hazards, both are specified, such as class 3 (flammable liquids) and class 6.1 (toxic substances) as subsidiary risks to a primary class 8 corrosive material, determined by precedence rules that prioritize the most severe hazard as primary.[34]Under UN standards, labeling ensures clear communication of these hazards through diamond-shaped labels affixed to packages. Each label displays the relevant hazard symbol in the upper portion, with the class or division number in the lower corner; primary and subsidiary hazard labels must be applied, with subsidiary labels placed adjacent to the primary one. For bulk packagings and transport vehicles, placards replicate these labels on a larger scale (at least 250 mm per side), and an orange-colored panel or placard displays the UN number in bold black lettering for quick identification. Packages must also be marked with the UN number, proper shipping name, and consignor/consignee details to facilitate handling and traceability.[35]For Class 1 explosives, UN requirements mandate labels that include not only the division number but also a compatibility group letter (e.g., A for primary detonating explosives, S for very insensitive substances) to prevent incompatible mixing during storage or transport.[35]The UN number serves as a key identifier for emergency response, linking directly to specialized information in tools like Transport Emergency Cards (TREM cards) under the European Agreement concerning the International Carriage of Dangerous Goods by Road (ADR), which detail hazards, firefighting measures, spillage procedures, and protective equipment based on the substance's classification.
Regional Variations
NA Numbers in North America
In North America, NA numbers serve as identification codes for hazardous materials that do not align perfectly with the international UN system, allowing for domestic exceptions in classification and transport requirements. These numbers are prefixed with "NA" followed by a four-digit code and are primarily used for substances requiring regional adaptations, such as combustible liquids with flash points between 60°C and 93°C, which fall outside stricter international flammable liquid criteria. For instance, NA 1993 designates "Combustible liquid, n.o.s." (not otherwise specified), enabling the transport of materials like certain diesel fuels or paints that would otherwise be unregulated or misclassified under UN standards. Similarly, NA 2212 identifies asbestos, particularly amphibole varieties, as a miscellaneous dangerous substance under Class 9, accommodating North American regulatory needs for handling this carcinogen in domestic shipments.[10][36][37]The NA numbering system spans from NA 0001 to NA 9999, though assignments are concentrated in the NA 9000 to NA 9279 range for these exceptions, reflecting a structured allocation to avoid overlap with UN numbers (UN 0001 to UN 9999). This range ensures distinct identification for materials unique to North American contexts, such as environmental hazards or substances with modified packing groups not recognized globally. The Pipeline and Hazardous Materials Safety Administration (PHMSA) under the U.S. Department of Transportation maintains the official Hazardous Materials Table in 49 CFR 172.101, where NA entries are listed alongside UN numbers, specifying hazard classes, packing groups, and special provisions.[10][38]In Canada, the Transportation of Dangerous Goods (TDG) Directorate of Transport Canada oversees similar implementations, harmonizing NA numbers with PHMSA regulations to facilitate cross-border transport while permitting variances like elevated flash point thresholds for Class 3 materials. This coordination stems from bilateral agreements ensuring reciprocity, where NA numbers are accepted for shipments to and from Canada but must conform to TDG Schedule 1 for domestic Canadian movements. PHMSA and TDG collaborate on updates to maintain alignment with the UN Model Regulations, yet retain flexibility for regional differences, such as treating certain low-hazard wastes differently.[39]NA numbers are mandatory for shipping documents, placards, and labels in the United States and for compatible cross-border operations with Canada, but they hold no international validity beyond North America, requiring conversion to UN equivalents for global shipments. This domestic focus enhances safety by tailoring regulations to local industries, such as oil and mining, without disrupting international trade flows.[10][39]
Other Non-UN Identifiers
In air transport, the International Air Transport Association (IATA) employs specific identifiers outside the standard UN numbering system for certain low-hazard materials, particularly consumer commodities. ID 8000 designates "Consumer commodity," a Class 9 miscellaneous hazardous material classification used for small quantities of everyday items containing limited amounts of dangerous goods, such as aerosols, paints, or polishes, that meet defined packaging and quantity limits under IATA Dangerous Goods Regulations.[40] This identifier simplifies shipping by allowing these items to be treated as a single entry rather than individual UN numbers, but it applies only to air transport and excludes forbidden goods like certain corrosives or toxics.[41]In European rail transport, the Regulations concerning the International Carriage of Dangerous Goods by Rail (RID) primarily align with UN numbers but incorporate additional regional codes, such as hazard identification numbers (also known as Kemler codes), for placarding and emergency response. These are two- or three-digit codes (e.g., 30 for flammable liquids or 80 for miscellaneous hazards) that supplement the UN number on vehicles and packages, providing quick visual indication of primary and subsidiary risks without replacing the UN system.[42] RID also includes addenda like special provisions or tank codes specific to rail operations, ensuring compatibility with the broader UN framework while addressing mode-specific requirements.[43]Limited-use identifiers, often provisional or mode-specific, are assigned for niche applications where standard UN numbers may not fully apply, such as certain aviation-regulated substances. These identifiers are distinct from core UN numbers, as they cater to exceptions like low-hazard or provisional shipments in aviation, where full UN protocols might be overly restrictive, and they are not valid across all transport modes or regions.[44]
Regulations and Usage
UN Model Regulations
The UN Model Regulations, formally titled Recommendations on the Transport of Dangerous Goods: Model Regulations, form the core international framework for assigning and applying UN numbers to dangerous goods during transport. Known informally as the "Orange Book" for its distinctive cover, this document establishes standardized criteria for classification, packaging, marking, labeling, and documentation to mitigate risks associated with hazardous materials. The 24th revised edition, published in 2025, reflects ongoing adaptations to technological and safety advancements while maintaining global harmonization.[7][45]Central to the Model Regulations is the dangerous goods list in Chapter 3.2, which catalogs all assigned UN numbers—over 3,000—alongside their proper shipping names, hazard classes, packing groups, special provisions, and instructions for safe handling. For each UN number, the regulations specify performance-based requirements for packagings (e.g., UN-approved drums, boxes, or intermediate bulk containers), compatibility with substances, and documentation such as the dangerous goods declaration. These elements ensure that transport operations across modes prioritize containment, segregation, and emergency response.[45]Biennial revisions are managed by the United Nations Economic Commission for Europe (UNECE) via its Sub-Committee of Experts on the Transport of Dangerous Goods, incorporating input from member states and international organizations to address emerging hazards. The 2025 edition (Rev. 24) introduces 11 new UN numbers, including UN 3551 and UN 3552 for sodium ion batteries, and revises entries for lithium batteries to accommodate hybrid variants containing both lithium-ion and sodium-ion cells, along with updated provisions for their transport in equipment or as cargo. Additional changes cover liquid organic hydrogen carriers, salvage pressure receptacles, and packaging for solid substances liable to liquefy during transit.[7][46][47]As a non-binding instrument, the Model Regulations provide a voluntary template that over 50 countries have incorporated into their domestic laws, either directly or through regional agreements like the European Agreement concerning the International Carriage of Dangerous Goods by Road (ADR), promoting seamless cross-border transport. This adoption extends to all major modes—road, rail, sea, and air—though specific implementations vary.[48]
Implementation Across Transport Modes
UN numbers are integral to the safe transport of dangerous goods across various modes, with sector-specific regulations adapting the core UN classifications to address unique operational risks and requirements. In road and rail transport in Europe, the European Agreement concerning the International Carriage of Dangerous Goods by Road (ADR) and Regulations concerning the International Carriage of Dangerous Goods by Rail (RID) mandate the use of UN numbers for classification, packaging, and labeling, with the 2025 edition introducing updated provisions for lithium and sodium ion batteries, including exemptions for batteries installed in vehicles and special packing instructions to mitigate thermal runaway risks.[49] In the United States, the Pipeline and Hazardous Materials Safety Administration (PHMSA) enforces UN number requirements through 49 CFR Parts 100-185, which cover identification, hazard communication, and packaging for highway and rail shipments, ensuring compatibility with international standards while incorporating domestic variations.[38]For maritime transport, the International Maritime Dangerous Goods (IMDG) Code, administered by the International Maritime Organization (IMO), requires UN numbers to classify and declare cargoes, with Amendment 42-24 (effective 2025-2026) aligning closely with the 24th revised edition of the UN Model Regulations by incorporating updated hazard classes, segregation rules, and provisions for elevated temperature substances. This alignment ensures consistent application of UN numbers on shipping documents, container markings, and stowage plans, emphasizing precautions against corrosion and reactivity in marine environments. In air transport, the International Air Transport Association (IATA) Dangerous Goods Regulations (DGR) 66th edition (2025) stipulate UN numbers for all air cargo and passenger shipments, introducing enhanced restrictions on undeclared devices containing lithium batteries to prevent fire hazards, including mandatory state-of-charge limits and prohibitions on certain damaged or recalled items.[50]Multimodal shipments benefit from the harmonized framework of the UN Model Regulations, which provide a baseline for UN number usage across modes, but require adaptations for specific conditions; for instance, UN 3480 designates lithium ion batteries, necessitating mode-tailored packaging such as UN-tested boxes for air with cushioning to limit short-circuiting, or ventilated containers for sea to manage off-gassing.[7] Enforcement of these implementations varies by jurisdiction and mode but generally involves civil penalties for violations, including fines up to $102,348 per violation per day for knowing non-compliance under U.S. law, with PHMSA and modal agencies like the Federal Motor Carrier Safety Administration conducting inspections and audits.[51] Training is a key enforcement element, as mandated by 49 CFR 172.704, requiring hazmat employees to complete general awareness, function-specific, safety, and security training every three years to ensure proper handling of UN-numbered materials.[52]