Classification and Shipping Description of Hazardous Materials Prepared by Prokopis A. Christou, PE, CHMM Rev. 4/24/2007

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1 Classification and Shipping Description of Hazardous Materials Prepared by Prokopis A. Christou, PE, CHMM Rev. 4/24/2007 The Hazmat 101 Web(tm) Permission to use this document is granted to individuals for individual, non-commercial, non-profit use only. All rights reserved. Use this workbook with copies of 49 CFR or copies of pages of the HM Table and Appendices. The BOE 6000 Traffic version of the HMR is available from: Introduction Unlike a product trade or brand name, the basic shipping description is a "name" that reveals the hazards of the materials contained in the package. Shippers use the basic shipping description to select the correct marks and labels for packages and placards for vehicles. Shippers also write the DOT shipping description on the shipping papers (e.g., bill of lading, waste manifest) for all hazardous materials. The DOT shipping description consists of the basic shipping description PLUS additional description if applicable. The DOT shipping description is designed to help the emergency responder identify the hazards of a material in the event of an incident. While shippers rely on the manufacturer to determine the correct basic shipping description, shippers are responsible to provide the required information and prepare the hazardous material shipment in compliance with the hazardous materials regulations (HMR). The basic shipping description has four components. The components tell us about the hazardous material. Component Where to find it Proper Shipping Name HMT Column 2 Hazard class, primary and subsidiary HMT Column 3 (subsidiary in Column 6) Identification Number HMT Column 4 Packing Group HM Column 5 *HMT: Hazardous Materials Table Hazard Classes and Packing Groups Manufacturers either test their products or rely on published data to determine the specific hazards of their materials. The HMR specifies nine classes of hazards, with specific criteria that must be met for the material to be included in the class, plus a class called Other Regulated Materials: Class 1 Explosives Class 2 Compressed Gases Class 3 Flammable Liquids Class 4 Flammable Solids Class 5 Oxidizers and Organic Peroxides Class 6 Toxic and Infectious Substances Class 7 Radioactive Materials Class 8 Corrosives Class 9 Miscellaneous Hazardous Material 1

2 ORM Other Regulated (hazardous) Material Some of the hazard classes are subdivided into divisions to provide a more precise indication of the hazard. For example, within Class 2 compressed gases, there are flammable gases (Division 2.1), oxidizing gases (Division 2.2), and nonhazardous gases (Division 2.3). Some materials have more than one hazard associated with them. The most significant hazard is called the primary hazard. Any other hazards are called subsidiary or secondary hazards. For example, a material may be both corrosive (class 8) and a flammable liquid (class 3). Choosing which hazard is the primary and which is the subsidiary is determined in accordance with the Precedence of Hazard Table in the HMR. For example, a class 8 (corrosive) PG II hazard takes precedence over a Class 3 (flammable liquid) PG III. Packing Groups In addition to hazard classes and divisions, the HMR uses packing group to identify the level of hazard. There are three packing groups: I, II, and III. Packing group I (PG I) is the most hazardous and PG III is the least hazardous. Highlights of Some of the Hazard Classes Class 2 - Gases Class 2 gases are substances that are gaseous, a mixture of gases, an article charged with a gas, or an aerosol. There are no packing groups for Class 2 materials. Division 2.1, Flammable gas (e.g., propane, butane) Division 2.2, Non-flammable gas and nonpoisonous gas (e.g., compressed air) Division 2.3, Gas poisonous by inhalation (e.g., sulfur dioxide, chlorine) Class 3 - Flammable Liquids Class 3 flammable liquids are materials that have a flash point no greater than 140 ºC. The flash point of a substance is listed on its material safety data sheet (MSDS). Packing groups for Class 3 materials are shown in the table below. The lower the flash point and boiling point, the more flammable the material is, meaning the greater the level of hazard. Flash point is the temperature at which a liquid gives off sufficient vapor to ignite in the presence of a source of ignition. Packing Group for Class 3 Flammable Liquids Packing Group Flash Point Boiling Point I ºC (95 ºF) II < 23 ºC (73 ºF) > 35 ºC (95 ºC) III 23 ºC (73 ºF) 60 ºC (140 ºF) > 35 ºC (95 ºC) *Note: The upper limit was changed to 140 ºF from 141 ºF for consistency with globally harmonized standards. For grandfather provisions, see (g) Class 6 - Poisonous Material and Infectious Substance Class 6 toxic materials and infectious substances are substances that are extremely toxic if swallowed, inhaled or contacted by skin, or are infectious. Class 6.1 Poisonous through inhalation of its vapors, by skin contact or by ingestion (e.g., methylene chloride) Class 6.2 Hazardous to animals, humans or both (e.g., rabies, blood samples of persons with HIV) 2

3 Packing groups for Division 6.1 materials are shown in the table below. LD50 means lethal dose and LC50 means lethal concentration. The lower the number, the more hazardous the material. LD and LC are provided in terms of milligrams of material per kilogram of body weight (mg/kg). Packing Group Packing Groups for Class 6.1 Poisonous Materials Dermal Toxicity LD50 (mg/kg) Oral Toxicity LD50 (mg/kg) Inhalation Toxicity Dust and Mist LC50 (mg/kg) I II > 5.0, 50 > 50, 200 > 0.2, 2 II Solids: > 50, 200 Liquids: > > 200, 1000 > 2, 4.0 * DOT revised the classification criteria. For grandfather provisions, see (g). Class 8 - Corrosives Class 8 corrosives are substances that destroy living tissue on contact or have a corrosion rate greater than 6.25 mm per year at 55 ºC (e.g., battery acid, sulfuric acid, industrial cleaners, sodium hydroxide). There are no divisions for Class 8. Packing groups for class 8 materials are shown in the table below. Packing Group I II III Packing Groups for Class 8 corrosive materials Description of Corrosive effect Material that causes visible destruction of skin tissue with an exposure time of 3 minutes or less (visible within 60 minutes) Material that causes visible destruction of skin tissue with an exposure time of > 3 minutes and 60 minutes (visible within 14 days). Material that causes visible destruction of skin tissue with an exposure time of > 60 minutes and 4 hours (visible within 14 days), OR that corrodes steel or aluminum at a rate > 6.25 mm (0.25 in) per year Class 9 - Miscellaneous Products, Substances Class 9 miscellaneous products, substances or organisms are substances that are hazardous materials even though they do not meet the criteria for inclusion in classes 1 to 8. Included in Class 9 are hazardous substances, hazardous waste, and marine pollutants that do not meet another hazard class. There are no divisions for Class 9. Packing groups for class 9 materials are listed in the Hazardous Materials Table (HMT) rather than by specific criteria. Other Regulated Materials (ORM) The ORM-D designation indicates a material, such as a consumer commodity or limited quantity, that is a hazardous material but presents only a limited hazard during transportation due to its form, quantity and packaging. There are no packing groups for ORM-D materials. Other Designations Hazardous substances. Substances listed in Appendix A to the HMT. Each substance is assigned a Reportable Quantity (RQ). For example, Ethylene Dichloride has an RQ of 100 pound. Marine pollutants - Substances listed in Appendix B to the HMT. Proper Shipping Name The proper shipping name (PSN) is a specific name assigned to a hazardous material. Manufacturers and shippers use a specific procedure detailed in the HMR when identifying the proper shipping name for a hazardous material. The Proper Shipping Name must be one that best describes the hazard and is selected from the HMT. 3

4 Example: "Sodium hydroxide solution" is a proper shipping name, Caustic Soda is a product name but it is not a Proper Shipping Name. If you are re-shipping hazardous materials, use the proper shipping name provided by the manufacturer (listed on the MSDS or original shipping paper), UNLESS you have changed the hazardous characteristic of the products or you know that the information is not accurate. Identification Number (UN/NA Number) The identification number is a unique 4-digit number used to identify a hazardous material. The identification number is located in the HM Table in the HMR. There is an identification number for every proper shipping name in the table. The 4-digit number is preceded by "UN" (United Nations) or "NA" (North America). Example: UN 1090 is the identification number for Acetone. Hazardous Materials Table The Hazardous Materials Table, or HMT, is the backbone of the Hazardous Materials Regulations. Understanding and knowing how to use the HMT is the first step toward compliance. You can find it the regulations at 49 CFR For each material listed, the HMT identifies each hazard class or specifies that the material is forbidden in transportation. It provides the proper shipping name of the material or directs the user to the preferred proper shipping name. In addition, the HMT specifies or references requirements pertaining to labeling, packaging, quantity limits aboard aircraft, and stowage of hazardous materials aboard vessels. The Hazardous Materials Table usually referred to as the HMT or the Table, governs the transportation of hazardous materials by all modes air, water, rail and highway. It is important to use the Hazardous Materials Table correctly. Column 1 Column 1 may contain any one of six symbols: +, A, D, G, I or W. + : fixes the proper shipping name, hazard class and packing group (you may not change them). A : material only regulated if offered or transported by aircraft, unless the material is a hazardous substance or a hazardous waste. Hazardous substances and/or hazardous wastes are regulated in all modes of transportation. D : proper shipping name appropriate for domestic (USA) transportation, may be inappropriate for international transportation (e.g., IMO, ICAO). G : generic proper shipping names for which technical names of the hazardous material must be included with the basic shipping description. I : proper shipping name appropriate for describing materials in international transportation (also acceptable for domestic). W : material is regulated only if offered or transported by vessel, unless the material is a hazardous substance or a hazardous waste. Hazardous substances or hazardous wastes are regulated in all modes of transportation. 4

5 The following codes are not part of the regulation but included in BOE 6000 Tariff version of HMR: R1, R2, R3, R4, R5: Material (pure substance) is a hazardous substance. RQ: R1=1 lb, R2= 10 lb; R3=100 lb, R4=1000 lb, R5= 5000 lb. P: Marine Pollutant PP: Severe Marine Pollutant. Column 2 Column 2 of the HMT contains the proper shipping name. Look closely at the two types of lettering, Roman and Italic. Proper shipping names are written in Roman type only. It is critical that the proper shipping name be spelled correctly on shipping papers. Entries in italics may not be used as PSNs. Qualifying words shown in italics are not part of the PSN. The words poison or poisonous may be used interchangeably with the word toxic when only domestic transportation is involved. When international transportation is involved, only the word toxic may be used. For a hazardous waste, the word waste must be placed before the PSN if waste is not included in the PSN. For example, Acetone would become Waste Acetone. Under certain conditions, a mixture or solution not identified specifically by name, comprised of a hazardous material identified in the HMT by technical name, and a non-hazardous material, must be described using the proper shipping name of the hazardous material and the qualifying word mixture or solution, as appropriate. Example: If the material was 100 percent Acetone, the best name would be Acetone. If the material was a flammable mixture and the single ingredient contributing to the hazard was acetone, the best name would be "Acetone mixture" or "Acetone solution." Where the HMT does not list a hazardous material specifically by its technical name, the proper shipping name is a generic proper shipping name. E.g., "Flammable liquids, n.o.s." is a generic PSN. Column 3 Column 3 of the HMT contains a designation of the hazard class or division corresponding to each proper shipping name, or the word Forbidden. Forbidden means that the material may not be offered for transportation or transported. This prohibition does not apply if the material is diluted, stabilized, or incorporated in a device, and it is classed in accordance with the definitions in Part 173 of the HMR. Column 4 Column 4 of the HMT lists the 4-digit identification number assigned to each proper shipping name. These 4-digit numbers provide quick identification of all hazardous materials. It is critical to emergency responders that the numbers are accurate and that they are correctly written and legibly displayed. Identification numbers preceded by UN for United Nations are descriptions of materials for domestic and/or international shipments, while identification numbers preceded by NA for North America may be used to describe certain materials when transported within the United States or between the United States and Canada. Column 5 Column 5 of the HMT specifies one or more packing groups assigned to a hazardous material. If a material is assigned to more than one packing group, the shipper must determine the correct packing group for the hazardous material. The packing group of the hazardous material will have an effect on a material s packaging requirements. This grouping is according to the relative degree of danger 5

6 presented by the hazardous material. Packing Group I indicates the greatest danger, while Packing Group II indicates a medium level of danger, and Packing Group III indicates a minor level of danger. The packing group number must be indicated in Roman numerals on shipping papers, when applicable, and may be preceded by the letters PG. There are no packing groups for Class 2, Class 7, Division 6.2, and ORMD materials. Column 6 Column 6 of the HMT specifies label codes, which represent the hazard warning labels required to be applied to each package of hazardous material, unless excepted. If two or more label codes are listed, the first represents the primary hazard and the others represent the subsidiary hazards. Column 7 Column 7 of the HMT specifies codes for special provisions applicable to packaging, packaging requirements, certification, and marking or labeling for a hazardous material, and inhalation hazards. Column 11 Column 11 does not exist in the regulations. It is included in the BOE 6000 Tariff version of HMR. The 3- digit code in that column represents the appropriate emergency response guide of the 2000 Emergency Response Guidebook. How to Classify Hazardous Materials If you are the shipper, you must determine if the material is regulated as a hazardous material and classify the material. Some options: 1. Review your advance classification lists. (See tip below.) 2. Use the HMR (49 CFR) 3. Use Chart 1 (of BOE 6000) and the HMR. 4. Use the manufacturer s current MSDS. Refer to the Transportation Section of the MSDS and verify that the information is accurate and that it complies with the HMR. Note. Make sure you use the most recent version of the MSDS. If the material meets any DOT hazardous class criteria, it is regulated as a (DOT) hazardous material. Then you must select the most appropriate Proper Shipping Name and the basic shipping description. Note: The term dangerous goods is used internationally in place of the US HMR term hazardous materials. Tip: Classify materials you frequently ship in advance, determine the required shipping description, markings, labels and placards and summarize the information in table for quick reference. This way, you and others don't have to "re-invent the wheel" each time you ship the materials. Basic Shipping Description [ ] The basic shipping description will consist of the following in exact sequence: Option 1- to be discontinued: (Remember SHIP) PSN - specified in Column 2 of the HMT. Hazard Class or Division # - specified in Column 3. If applicable, the subsidiary hazard class(es) or division # in parentheses -specified in Column 6. ID # (UN or NA #) - specified in column 4. 6

7 If applicable, the PG in Roman numerals -- specified in Column 5, preceded by the letters "PG" (e.g., PG II). Examples: One hazard class: Acetone, 3, UN1090, PG II. More than one hazard class: Cyclobutyl chloroformate, 6.1, (8,3), UN 2744, PG II. Note: This sequence, previously the preferred sequence, is discontinued effective 1/1/08. A six-year transition period is allowed for domestic shipments only until 1/1/13. Option 2. Now the only option: (Remember ISHiP) ID # (UN or NA #) - specified in column 4. PSN - specified in Column 2 of the HMT. Hazard Class or Division # - specified in Column 3. If applicable, the subsidiary hazard class(es) or division # in parentheses -specified in Column 6. If applicable, the PG in Roman numerals -- specified in Column 5, preceded by the letters "PG" (e.g., PG II). Examples: One hazard class: UN1090, Acetone, 3, UN1090, PG II. More than one hazard class: UN 2744, Cyclobutyl chloroformate, 6.1, (8,3), PG II. Note: This sequence was required by European Road Regulations (ADR). It was added to the HMR as an alternative and now is the mandatory option for he US and internationally. For the HMR, it is mandatory (subject to transition period) effective 1/1/08 and authorized as of 1/1/07. For shipping documents prepared in accordance with the ICAO Technical Instructions (shipments by air) and the IMDG Code (international shipments by water) it is mandatory beginning 1/1/07. Additional Shipping Description [ et al] Waste. For hazardous waste, where "waste" is not part of the PSN. Add "Waste" to precede PSN. Hazardous Substances. Except for Class 7 materials, if the proper shipping name for a material that is a hazardous substance does not identify the hazardous substance by name, the name of the hazardous substance shall be entered in parentheses in association with the basic shipping description. If the material contains two or more hazardous substances, at least two hazardous substances, including the two with the lowest Reportable Quantities (RQ), must be entered. For a hazardous waste, the waste code (e.g. D001), if appropriate may be used to identify the hazardous substance. In addition, the letters "RQ" shall be entered either before or after the shipping description for each hazardous substance. Note: The term Hazardous Substance comes from EPA release reporting regulations. 49 CFR incorporates EPA's list of hazardous substances as Appendix A to the HMT. For the purpose of 49 CFR a material or its constituent is a Hazardous Substance only if it is listed in Appendix A AND the quantity in the PACKAGE exceeds or equals its RQ. [Ref ] When in a mixture or solution For radionuclides, conforms to paragraph 7 of the appendix A to For other than radionuclides, is in a concentration by weight which equals or exceeds the concentration corresponding to the RQ of the material, as shown in the following table: 7

8 RQ pounds (kilograms) Concentration by weight Percent PPM 5000 (2270) , (454) , (45.4) , (4.54) (0.454) Caution: Remember to check for synonyms and constituents when checking Appendix A. Tip: In the BOE 6000, hazardous Substances (listed by technical name) are identified in column 1 as R1, R2, R3, R4, or R5. Marine Pollutants. This applies to all bulk shipments regardless of transportation mode, and non-bulk shipments by vessel (49 CFR 171.4). If the proper shipping name for a material which is a marine pollutant does not identify by name the component which makes it a Marine Pollutant, the name of that component must appear in parentheses in association with the basic shipping description. In addition, the words "Marine Pollutant" shall be entered in association with the basic shipping description. Marine Pollutants are listed in Appendix B. P: Marine pollutant. PP: Severe marine pollutant. Note: The term Marine Pollutant comes from the IMO (International Maritime Organization). For the purpose of 49 CFR, a material or its constituent is a Marine Pollutant only if it is listed in Appendix B AND the concentration in the PACKAGE exceeds or equals 10% b.w. for P, or 1% b.w. for PP. [Ref ] Caution: Remember to check for synonyms when checking Appendix B. Tip: In the BOE 6000, Marine Pollutants (listed by technical name) are identified in column 1 as P or PP. Technical names for "n.o.s" and other generic descriptions. For a material described by a generic proper shipping name, the technical name of the HM must be entered in parentheses in association with the basic shipping description. Technical and chemical group names shall be entered in parentheses between the proper shipping name and the hazard class, or follow the basic shipping description. For mixtures, the technical names for at least two components most predominantly contributing to the hazards are required. Technical names are not required for a material described with a proper shipping name "Hazardous waste, liquid or solid, n.o.s", classed as Miscellaneous Class 9, provided the EPA hazardous waste number is included in association with the basic shipping description (E.g., D001). Empty packaging. For a tank car containing residue of an HM, the words "RESIDUE: Last contained ***" must be entered before the basic shipping description of the HM last contained in the tank car. The additional description for other type of containers is optional. (The company recommends that it be included for all containers.) Example: "RESIDUE: Last contained UN 1255, Naphtha, Class 3, PG II." Poisonous materials. If a liquid or solid Division 6.1 (primary or subsidiary) PG I or II-add "Poison" or "Toxic" if the PSN or Class/Division does not disclose the material as poison. If PIH, "Poison-Inhalation Hazard" or "Toxic-Inhalation Hazard" and the words "Zone A", "Zone B", "Zone C", or "Zone D", for gases or "Zone A" or "Zone B" for liquids, as appropriate, shall be entered on the shipping paper immediately 8

9 following the shipping description. "Poison" or "Toxic" need not be repeated if already shipping description. If applicable, the Hazard Zone is specified by Special Provision in Column 7 of the HMT. Note: "Poison" versus "toxic", "poisonous" versus "toxic". Either one is acceptable for domestic transportation. Only "toxic" must be used for domestic transportation (e.g., IATA, IMDG). Others situations. Include but are not limited to the following if applicable: special permits, limited quantities, radioactive materials, transportation by air, transportation by rail, transportation by highway, transportation by water, dangerous when wet materials, elevated temperature materials, organic peroxides, self reactive materials, samples. ERG. It is recommended that the Emergency Response Guide number listed for the material in DOT's Emergency Response Guidebook be included as additional shipping description after all mandatory DOT description in the format: ERG# ***. Example: UN1090, Acetone, 3, PG II, RQ, ERG# 127. Product name product codes: Recommended. Must be included after all mandatory DOT description. Shipping Papers Unless excepted, the material must be described in a shipping paper as required by the HMR. Additional information may be entered on the shipping paper if it does it not conflict with the HMR. Not DOT regulated information must not be mixed with DOT shipping description, it can be added after the required DOT shipping description. The information on the shipping paper must be legible, in English and meet the requirements of the HM Regulations. The shipping paper must include: For each HM: Basic shipping description Additional shipping description if applicable Total quantity Number and type of packaging. The total quantity must be indicated (by mass or volume, or by activity for Class 7 materials) and must include the unit of measurement. For example, "200 kgs." or "50 L." The type of packages must be indicated by description of the package (for example, "12 drums"). Indication of the packaging specification number ("1H1") may be included in the description of the package (for example, "12 1H1 drums" or "12 drums (UN 1A1)." Example: 12 Drums, 3000 Pounds, UN 2744, Cyclobutyl chloroformate, 6.1, (8,3), PG II, ERG# 155. Name of the shipper and address. The words "EMERGENCY CONTACT ****" with the 24 hour emergency response telephone number. More than one telephone number may be listed. Consecutive page number of total pages (e.g. Page 1 of 4), if applicable. Shipper's certification (see 49 CFR ) and signature. (Note: there is an additional certification for shipments by air. Note: The additional shipping description must be indeed in association with the basic shipping descriptions. There are some options, but it general it must not be intermixed within the basic shipping description. 9

10 You must not use abbreviations for shipping description. DOT allows certain standard abbreviations for unit of measurements and types of containers. Ounce = oz. Gallon = gal. Pound = lb. Liter = L Gram = g. Quart = qt. Kilogram = kg. Pint = pt. Hazardous waste manifests must be used as the shipping papers for shipments of hazardous waste. Shipper s certification Domestic version This is to certify that the above-named materials are properly classified, described, packaged, marked and labeled, and are in proper condition for transportation according to the applicable regulations of the Department of Transportation. International version (good for domestic too) I hereby declare that the contents of this consignment are fully and accurately described above by the proper shipping name, and are classified, packaged, marked and labeled/placarded, and are in all respects in proper condition for transport according to applicable international and national governmental regulations. International version for air shipments I hereby certify that the contents of this consignment are fully and accurately described above by proper shipping name and are classified, packaged, marked and labeled, and in proper condition for carriage by air according to applicable national government regulations. Additional certification language for shipments by air I declare that all of the applicable air transport requirements have been met. Retention of Shipping Papers Hazardous waste--3 or 5 years (varies by state). Shipments accepted on or after 1/9/06--at least 2 years. Shipments accepted before 1/9/06--at least 375 days. 10

11 Hazardous Materials Table

12 Shipping Description Examples Material: 1 Quantity, number and type of containers 2 UN/NA ID # 3 Proper shipping name 4 Numeric primary hazard class/div and subsidiary in parentheses 5 PG # 6 "RQ" w/technical in parentheses names or waste codes if generic PSN. 7 "Marine Pollutant" w/technical names in parentheses if generic PSN. 8 "Poison" if applicable 9 Poison-Inhalation Hazard zone information if applicable 10 Other required information 11 "ERG XXX" 12 Emergency Contact Phone # Material: 1 Quantity, number and type of containers 2 UN/NA ID # 3 Proper shipping name 4 Numeric primary hazard class/div and subsidiary in parentheses 5 PG # 6 "RQ" w/technical in parentheses names or waste codes if generic PSN. 7 "Marine Pollutant" w/technical names in parentheses if generic PSN. 8 "Poison" if applicable 9 Poison-Inhalation Hazard zone information if applicable 10 Other required information 11 "ERG XXX" 12 Emergency Contact Phone #