VDEM Hazardous Materials Technician Course PDF

VDEM Hazardous Materials Technician Course Module 1: Introduction to HAZMAT Response Regulations and Standards OSHA 1910.120 (q) (6) (iii) Hazardous Material Technicians (HMT) are individuals who respond to releases or potential releases for the purpose of stopping the release. They assume a more aggressive role than the first responder at the operations level in that they will approach the point of release in order to plug, patch or otherwise stop the release of a hazardous substance. NFPA 472 Chapter 7 The Hazardous Material Technician (HMT) shall be that person who responds to hazardous material/WMD incidents using a risk-based response process by which he or she analyzes a problem involving hazardous material/WMD, selects applicable decontamination procedures, and controls a release using specialized protective clothing and control equipment. The HMT shall demonstrate the following competencies:  Understand the roles and responsibilities of the HMT when responding to and operating at an incident involving hazardous material/WMD.  Understand the various terms and definitions used by government agencies to identify and describe hazardous materials.  Understand state and federal laws and regulations as they apply to emergency operations at an incident involving hazardous material/WMD. Version: March, 2018 Page | 1 Module 1: Introduction to HAZMAT Response INTRODUCTION: The Hazardous Materials Technician Course is the third step in the Commonwealth of Virginia Hazardous Materials Training Program. The program is designed to prepare emergency personnel for incidents involving the release or potential release of hazardous materials. The Hazardous Materials Training Program is broken into three broad areas based on the types of skill that are required of the responder. These areas are called defensive positions, offensive positions, and management positions. HM IC Incident Management HM Branch Branch Management HM Safety Safety HM Specialist Offensive Tactics Product, Container HM Technician Environment Defensive Tactics HM Operations Isolate/Evacuate Control Product HM Awareness Movement During the first two courses, Hazardous Materials First Responder – Awareness and HMFR – Operation, the students were taught to take a defensive position in mitigating the incident. At these levels, the responder is likely to be the first on the scene of a hazardous materials incident. The first responder at Awareness and Operations is limited, and the primary duty is to survey the immediate area and minimize the potential harm of an unplanned release of hazardous materials. Upon completion of this course, the student will now be able to take an offensive position when dealing with an incident. The Hazardous Materials Technician is expected to assume a more aggressive role in the controlling of a hazardous materials incident. The Hazardous Material Technician Course will provide the technician with the knowledge and skills needed to identify and analyze a HM/WMD incident, approach the point of release to plug, patch, or otherwise control the release of a hazardous substance, and reduce their harmful effects. As such technician level training relies heavily upon the basic skills the responders acquired at the Awareness and Operations level. The Hazardous Materials Technician Course is designed to meet the performance objectives as outlined in NFPA 472 and 29 CFR Part 1910.120(q) (iii). Version: March, 2018 Page | 2 Module 1: Introduction to HAZMAT Response The goal of the Hazardous Materials Technician Course is to properly train personnel so they may operate in a safe and effective manner at a hazardous materials incident, according to government regulations and professional standards. There are three major objectives to meet the goals of the Hazardous Materials Technician: 1. Analyze a hazardous materials incident to determine the magnitude of the problem in terms of outcomes.  Survey the hazardous materials incident to identify special containers involved, to identify or classify unknown materials, and to verify the presence and concentrations of hazardous materials through the use of monitoring equipment.  Collect and interpret hazard and response information from printed resources, technical resources, computer databases, and monitoring equipment.  Determine the extent of damage to containers.  Predict the likely behavior of materials when released.  Estimate the size of an endangered area using computer modeling, monitoring equipment, or specialists in this area. 2. Plan a response within the capabilities of available personnel, personal protective equipment, and control equipment.  Identify the response objectives for hazardous materials incidents.  Identify the potential action options available to meet the response objectives.  Select the personal protective equipment required for a given action option.  Select the appropriate decontamination procedures. Version: March, 2018 Page | 3 Module 1: Introduction to HAZMAT Response  Develop a tactical plan of action, including safety considerations, consistent with the local emergency response plan and the organization’s Standard Operating Procedures, and within the capability of the available personnel, personal protective equipment, and control equipment. 3. Implement the planned response to favorably change the outcomes consistent with the organization’s standard operating procedures and/or a site safety plan.  Perform the duties of an assigned position within the local incident management system (IMS).  Don, work in, and doff appropriate personal protective clothing including, but not limited to, both liquid splash and vapor protective clothing with appropriate respiratory protection.  Perform the control functions assigned in the plan of action. HAZARDOUS MATERIALS REGULATIONS AND DEFINITIONS Numerous terms are used to describe hazardous materials. Each definition is specific depending upon who is using the term and when it is used. Be careful because each definition has a different meaning: Federal Laws and Regulations  Resource Conservation and Recovery Act of 1976 (RCRA) 42 U.S.C. §6901 et seq. RCRA established the federal effort in regulating solid and hazardous waste management. Specific tasks include:  Defines solid and hazardous waste Version: March, 2018 Page | 4 Module 1: Introduction to HAZMAT Response  Regulates the generation, storage, transportation, treatment and disposal of hazardous waste  Establishes a permit program for hazardous waste treatment, storage, and disposal facilities (TSDs) RCRA is also known as the “Cradle to Grave Law”. The law exempts actions taken during the immediate response. Transportation, storage, and disposal of material after it is cleaned-up are subject to all RCRA permitting.  Comprehensive Environmental Response, Compensation, and Liability Act of 1980 (CERCLA) 42 U.S.C. §9601 et seq. CERCLA established the Superfund hazardous substances clean-up program. Specific tasks include:  Requires the clean-up of releases of hazardous substances  Authorizes the federal government to respond to spills and other releases  Defines “Responsible Parties” The law exempts actions taken by State and local governments from CERCLA liability during an emergency response.  Superfund Amendments and Reauthorization Act of 1986 (SARA) Title I - 42 U.S.C. section 126  Requires OSHA to establish health and safety standards for workers who handle or respond to chemical emergencies. Title III - 42 U.S.C. section 300  Emergency Planning and community right to know.  Contingency plans for hazardous substances. Version: March, 2018 Page | 5 Module 1: Introduction to HAZMAT Response Federal Definitions  Hazardous Materials (as found in 49 CFR) U.S. Department of Transportation (DOT) “A substance or material which has been determined by the Secretary of Transportation to be capable of posing an unreasonable risk to health, safety, and property when transported in commerce, and which has been so designated…”  Hazardous Substances (as found in 29 CFR) Occupational Safety & Health Administration (OSHA) “Any substance designated or listed under paragraphs (a) through (d) of this definition, exposure to which results or may result in adverse effects on the health or safety of employees:  Any substance defined under Section 101(14) or the Comprehensive Environmental Response, Compensation and Liability Act (CERCLA);  Any biological agent or other disease causing agent as defined in Section 101(33) of CERCLA;  Any substance listed by the U.S. Department of Transportation as hazardous materials under 49 CFR 172.101 and appendices; and (d) hazardous waste as herein defined…” Version: March, 2018 Page | 6 Module 1: Introduction to HAZMAT Response  Hazardous Substances (as found in 40 CFR) US Environmental Protection Agency (US EPA) “Any substance listed in 40 CFR Table 302.4 that, when released into the environment above a certain amount, must be reported and, depending upon the threat to the environment, federal involvement may be authorized…”  Extremely Hazardous Substance US Environmental Protection Agency (US EPA) A term used to describe substances listed in 40 CFR, part 355, appendices A & B. These chemicals may be subject to emergency planning and, in the event of a release, emergency notification.  Hazardous Waste US Environmental Protection Agency (US EPA) A term for chemicals that are regulated under the Resource, Conservation and Recovery Act (RCRA) (40 CFR, part 261.33) “Cradle to Grave Law.” Hazardous wastes in transport are regulated by DOT (49 CFR, parts 170-179).  Additional Terms for Hazardous Materials Toxic Chemicals EPA term for chemicals whose total emission must be reported annually. Highly Hazardous Chemicals OSHA term for materials covered under 29CFR 1910.119 ‘Process Safety Management’. Dangerous Goods Term used by Transport Canada and the National Fire Protection Agency (NFPA) Version: March, 2018 Page | 7 Module 1: Introduction to HAZMAT Response “Outside the United States, the term ‘dangerous goods’ is used as roughly the equivalent to our usage of the term hazardous materials, especially as it relates to regulations governing transportation of materials (goods). The regulations are international and were prepared by the Committee of Experts on the Transportation of Dangerous Goods for the United Nations…”  Weapons of Mass Destruction (WMD) 18 USC section 2332a  Any destructive device as defined by section 921 of this title; includes explosives, incendiaries, and projectiles.  Any weapon designed or intended to cause death or serious bodily injury through the release, dissemination, or impact of toxic or poisonous chemicals; or their precursors.  Any weapon involving a biological agent, toxin or vector.  Any weapon that is designed to release radiation or radioactivity at a level dangerous to human life. State Laws and Regulations  Code of Virginia *44-146.34 of the Virginia Code Hazardous Materials means substances or materials which may pose unreasonable risks to health, safety, property or the environment when used, transported, stored or disposed of, which may include materials which are solid, liquid, or gas. Hazardous materials may include toxic substances, flammable and ignitable materials, explosives, corrosive materials, and radioactive materials, and include  Those substances or materials in a form of quantity which may pose an unreasonable risk to health, safety, or property when transported, and which the Secretary of Transportation of the United States has so designated by regulation or order; Version: March, 2018 Page | 8 Module 1: Introduction to HAZMAT Response  Hazardous substances as defined or designated by law or regulation of the Commonwealth or State government;  Hazardous waste as defined or designated by law or regulation of the Commonwealth.  Weapon of Terrorism, Virginia Code Title 18.2-46.4 Any device or material that is designed, intended, or used to cause death, bodily injury or serious bodily harm, through the release, dissemination, or impact of (i) poisonous chemicals; (ii) an infectious biological substance; or (iii) release of radiation or radioactivity. Reference Materials: Emergency Services and Disaster Law, Title 44.146, Code of Virginia. Hazardous Materials – Managing the Incident, Noll and Hildebrand, Jones and Bartlett Learning, 4th edition, 2013. Hazardous Waste Operations and Emergency Response, Occupational Safety and Health Administration, 29 CFR 1910.120. Standard for Competence of Responders to Hazardous Materials/Weapons of Mass Destruction Incidents, National Fire Protection Association, Standard 472. Version: March, 2018 Page | 9 Module 1: Introduction to HAZMAT Response This page intentionally left blank. Version: March, 2018 Page | 10 Module 1: Introduction to HAZMAT Response REVIEW QUESTIONS MODULE 1: INTRODUCTION TO HAZMAT RESPONSE 1. Explain the role of the Hazardous Materials Technician at an incident involving hazardous material. 2. Identify and explain in detail each of the three major objectives that will meet the goals of a Hazardous Materials Technician. 3. Define the following terms: a. Hazardous Materials Under Virginia Code U.S. Department of Transportation b. Hazardous Substance EPA OSHA 4. Extremely Hazardous Substance 5. Hazardous Waste Version: March, 2018 Page | 11 Module 1: Introduction to HAZMAT Response 6. Dangerous Goods 7. Weapon of Mass Destruction (by Federal Law) 8. Define RCRA. What falls under its ruling? 9. Define CERCLA. What falls under its ruling? 10. Define SARA. What are the major parts of this law? Version: March, 2018 Page | 12 VDEM Hazardous Materials Technician Course Module 2: Safety Regulations and Standards OSHA 1910.120 (q) (6) (iii) (A) Know how to implement the employer’s emergency response plan. (B) Be able to function within an assigned role in the Incident Command System. NFPA 474 Chapter 7 7.3.5 Given scenarios involving HM/WMD incidents, the hazardous material technician shall develop a plan of action, including a safety and control plan that is consistent with the emergency response plan and standard operating procedures and within the capability of available personnel, personal protective equipment, and control equipment for that incident… 7.4.1 ‘…the hazardous material technician shall demonstrate the duties of an assigned function in the hazardous material branch or group within the incident command system and shall identify the role of the HMT during HM/WMD incidents.’ The HMT shall demonstrate the following competencies:  Know the basic safety procedures for handling emergency response to HM/WMD incidents.  Know the components of the HM incident Tactical and Safety Plan and explain what information is included in each component.  Identify and describe the functional positions in the HM Branch (Group) within the ICS. Version: March, 2018 Page | 13 Module 2: Safety Standard Safety Practices when Operating at a HazMat/WMD Incident Site safety practices should be implemented and strictly followed at every incident prior to all tactical control operations. Standard Safety Practices include:  Follow Standard Operational Procedures.  Receive and understand the site safety and tactical briefing.  Limit exposure to all hazards; Time – Distance - Shielding.  Maintain communications.  Identify and properly wear and use appropriate PPE.  Always work with the buddy system.  Always have a back-up crew prepared and standing by to assist entry personnel.  Establish and practice strict decontamination procedures. Safety Practices for all VDEM Hazardous Materials Training Practical Activities  Attend and understand the safety briefing.  Follow all instructor and Safety Officer directions.  Utilize the required safety equipment as identified in the safety briefing.  Stay with your assigned group or partner  Immediately report all injuries or problems to your instructor or safety officer.  In the event of an emergency during class the following emergency procedure will be followed:  Emergency Signal will sound - 3 five second blasts of the air horn.  All students and instructors will immediately cease all practical activities.  All students and instructors will report to the muster point identified in the safety briefing.  Personnel will be given further information and instructions. Version: March, 2018 Page | 14 Module 2: Safety Overview of safety requirements based on Hazardous Waste Operations and Emergency Response Regulations (HAZWOPER) 29CFR 1910.120 (q) “The safety and security of response personnel and others in an area of an emergency response incident site should be of primary concern to the incident commander. The use of a site safety plan could greatly assist those in charge of assuring the safety and health of responders on the site.” (OSHA 1910.120) “Emergency response means a response effort by employees from outside the immediate release area or by other designated responders (i.e., mutual aid groups, local fire departments, etc.) to an occurrence which results, or is likely to result, in an uncontrolled release of a hazardous substance.” “…covers employers whose employees are engaged in emergency response no matter where it occurs…” NOTE: THIS IS A BRIEF SUMMARY AND NOT THE EXACT WORDING OF THE OSHA REGULATIONS. Emergency Response Program to Hazardous Substance Releases. 29 CFR 1910.120(q) (1)  An emergency response plan shall be developed and implemented to handle anticipated emergencies prior to the commencement of emergency response operations…”  The plan shall be in writing and available for inspection and copying. Elements of an emergency response plan. 29 CFR 1910.120(q) (2)  Pre-emergency planning and coordination with outside parties.  Personnel roles, lines of authority, training, and communications.  Emergency recognition and prevention.  Safe distances and places of refuge.  Site security and control. Version: March, 2018 Page | 15 Module 2: Safety  Evacuation routes and procedures.  Decontamination  Emergency medical treatment and first aid  Emergency alerting and response procedures.  Critique of response and follow-up.  PPE and emergency equipment. Emergency response organizations may use the local emergency response plan or the state of emergency response plan or both, as part of their emergency response plan to avoid duplication. Procedures for handling emergency response 29 CFR 1910.120 (q) (3)  The senior emergency response official responding to an emergency shall become the individual in charge (IC) of a site-specific incident command system (ICS).  The “senior official" at an emergency response is the most senior official on the site who has the responsibility for controlling the operations at the site.  Initially it is the senior officer on the first-due piece of responding emergency apparatus to arrive on the incident scene.  The IC shall identify all hazards substances or conditions present and shall address site analysis, use of engineering controls, maximum exposure limits, hazardous substance handling procedures, and use of new technologies.  Based on the hazardous substances and/or the conditions present, the individual in charge of ICS shall:  Implement appropriate emergency operations  Assure that the personal protective equipment (PPE) is appropriate for the hazards Version: March, 2018 Page | 16 Module 2: Safety  Employees engaged in emergency operations and exposed to an inhalation hazard or potential inhalation hazard shall wear positive-pressure self-contained breathing apparatus (SCBA).  Limit the number of emergency response personnel at the emergency site, in those areas of potential or actual exposure to incident or site hazards. Operations in hazardous areas shall be performed using the buddy system in groups of two or more.  Back-up personnel shall be standing by with equipment ready to provide assistance or rescue. Qualified basic life support personnel, as a minimum, shall also be standing by with medical equipment and transportation capability.  The IC shall designate a safety officer with specific responsibility to identify and evaluate hazards and provide direction with respect to the safety of operations.  When judged to be an IDLH and/or to involve an imminent danger condition, the Safety Officer shall have the authority to alter, suspend, or terminate those activities.  After emergency operations have terminated, the individual in charge of ICS shall implement appropriate decontamination procedures. Medical Surveillance Program 29 CFR 1910.120 (q) (9) refers to paragraph (f) Purpose - Hazardous materials response personnel may be exposed to high levels of stress, toxic chemicals, safety hazards, biological hazards, and radiation. For those individuals who face these life-threatening emergencies, a medical surveillance program is the cornerstone of an effective hazardous materials responder health and safety management system. In addition, OSHA 1910.120 requires hazardous materials employees to participate in a medical surveillance both before and during employment. Version: March, 2018 Page | 17 Module 2: Safety Types of medical examinations are as follows:  Pre-employment screening: Necessary for two reasons: A determination of fitness for duty, and Baseline data for future exposures. Information should include occupational and medical history, physical examination; tests, including blood and urine; x-rays; ability to perform while wearing protective clothing.  Annual medical exams: To compare sequential medical information with the baseline data to determine biologic trends that may mark early signs of adverse health effects. They should include interval medical history: additional medical testing, i.e. pulmonary function test, hearing test, vision test, blood and urine test when indicated.  Termination medical exam: At the end of employment with a response team, all personnel should have a medical exam as described in the pre-employment exam. This should account for the total biological effect accumulated during employment on the team. Emergency treatment: If, at any time during employment, a team member receives an acute exposure to either physical or chemical hazards on a site, he/she must be examined by a physician at the nearest emergency medical facility. Non-emergency exam: Pre-entry screening, which includes a full set of vitals to include weight and mental condition. Post-entry screening, which is the same as exam as Pre- entry screening, is also performed. Medical information from both screenings should be cross-referenced which each other and past screenings. Version: March, 2018 Page | 18 Module 2: Safety Chemical Protective Clothing 29 CFR 1910.120 (q) (10) Chemical protective clothing and equipment to be used by HAZMAT team members shall meet the requirements of paragraph (g) (3) through (5).  PPE shall be selected and used to protect employees form hazards and potential hazards as identified during the site characterization and analysis.  Requires that a Personal Protective Equipment Program shall be established. Post Emergency Response Operations 29 CFR 1910.120 (q) (11) refers to paragraph (b) through (o). Upon completion of the emergency response if it is deemed necessary to remove hazardous substances from the site the employer shall comply with all the requirements of paragraph (b) through (o). Hazardous Material Tactical and Safety Plan The Incident Commander (IC) is responsible to develop and implement the Incident Action Plan (IAP). Under the overall direction of the IC and to meet the objectives of the IAP the Hazardous Material Branch Director/Group Supervisor (HMBD) is responsible to develop and implement the Hazardous Material Tactical and Safety Plan (HMTSP).The HMTSP should be developed for each incident prior to the implementation of entry-level tactical control operations. All personnel operating in the HazMat Branch must be briefed and understand the HMTSP. Components of the Hazardous Material Tactical and Safety Plan 1. Site Map – is a graphic representation of the incident site. The site map should identify critical operational areas and incident facilities. It should include the following:  Control zones - Hot, Warm, Cold  Work areas  Decontamination area Version: March, 2018 Page | 19 Module 2: Safety  Access control points  Safe refuge areas  Hazard areas identified  Topography/physical layout  Incident facilities 2. Hazard Analysis – identifies incident hazards and provides a risk analysis of the hazards on the site.  Chemical hazards - identify chemical hazards and evaluate the risks associated with the chemical(s) involved. This should include:  Chemical name and properties  Concentration of chemical  Health hazards - toxicity levels and route of entry  Fire hazards - degree of combustibility and ignition potential  Reactivity hazards - chemical instability and reactivity with other materials  Physical hazards - identify other types of hazards and the degree of harm they present. These should include:  Energy sources  Mechanical hazards  Terrain  Confined spaces or limited access points Version: March, 2018 Page | 20 Module 2: Safety  Weather 3. Safety and Health Considerations – Identify the signs and symptoms of exposure to hazardous substances and the effects on responder health if they are contaminated or suffer a chemical injury. Identify the pre-hospital emergency care of contaminated patients at the basic and advanced life support level. This section should include:  Medical personnel with equipment and transportation should be on site.  Emergency medical procedures to be followed in case of injury or contamination. 4. Tactical Objectives – Identifies what objectives needs to be accomplished to control the hazards and protect life, critical systems, the environment and property. Determines the tactical operations that will be implemented.  Objectives must be met to mitigate the incident. These would be part of the action plan, but must be communicated to all responders on-site.  Standard Operating Procedures. Follow standard operating procedures and practices at all times. 5. Scene Control Zones  Based on the type and degree of hazards the criteria to establish control zones is established.  Identify the location of hazard area and control zones; Hot, Warm and Cold zones.  Identify the access and exit points for the hazard area and tactical operational areas. 6. Tactical Command Structure  Presents the ICS organizational chart of the Hazardous Material Branch. Version: March, 2018 Page | 21 Module 2: Safety  Identifies HM Branch functions activated and personnel and resources allocated to each functional position. 7. Site Communications  Designated radio communications  Personnel in Hot Zone should have constant communications with HM Branch Director, HazMat Safety Officer, Entry Supervisor and backup teams. This may be via radio on designated radio channels or by direct line of sight.  Emergency communications procedures should be established. These would include hand signals and horns, bells or sirens. 8. Hazard Monitoring  Monitoring equipment should be used to identify the types of hazards on site and to establish the hazard zone area.  Monitoring of hazards should include toxicity, flammability, oxygen concentration corrosiveness and radioactivity.  The monitoring plan should include types of equipment and instruments, location of monitoring, evaluation of instrument readings, and the criteria for action levels. 9. PPE - Identify ensemble level and type of protective equipment necessary for response personnel based on the site analysis and the hazards identified. 10. Decontamination  All personnel leaving the Hot Zone or those who have been exposed to chemical hazards shall be properly decontaminated.  Identify decontaminated locations and stages/procedures of decontamination. Version: March, 2018 Page | 22 Module 2: Safety Incident Command System - HazMat Branch or Group The Incident Command System (ICS) provides a standard system for managing an emergency incident. ICS Functional Elements COMMAND - responsible for the overall management of the incident. Develops and implements strategic decisions, approves the ordering and release of resources, responsible for incident safety, staff positions, Safety Officer, Information Officer and Liaison Officer. OPERATIONS - responsible for the direct management of all incident tactical activities, PLANNING - responsible for the collection, evaluation and dissemination of tactical information, including resource status, situation status, documentation and technical specialist LOGISTICS - responsible for providing all support services to the incident including rehabilitation, communications, supplies and facilities FINANCE - responsible for all financial procurement services and cost analysis. The IC or Operations Section Chief may not be a HAZMAT Technician or Specialist and therefore must delegate the tactical responsibility to a qualified and competent HAZMAT Branch Director or Group Supervisor. While the IC is ultimately responsible for the outcome of the incident, the HMBD will command and control all personnel working in the hazardous material operational area. HAZMAT Branch or Group Organization The Hazmat Branch works in the Operations Section. The HM Branch Director will be responsible to the Operations Section Chief (if activated) or the Incident commander. The HM Branch is established in the ICS to deal with all tactical operations involving hazardous materials at an incident. Depending on the scope and complexity of the incident hazmat functions may be performed at different levels in the ICS. As an example, in a situation where the only tactical problem is the control of a hazmat leak and spill, with no exposures, the Hazmat function may be the only tactical function at Version: March, 2018 Page | 23 Module 2: Safety the incident. In other situations, an incident may require fire control, medical care for large number of citizens and evacuation. In this command structure the hazmat function may be at the Branch or Group level. No matter what the size and complexity of the incident if hazardous materials are involved there are certain tactical functions that must be performed. The purpose of this section is to define the tactical organization by functional position working under the command of the Hazmat officer. HAZMAT BRANCH DIRECTOR (GROUP SUPERVISOR) The Hazmat Branch Director (or Group Supervisor depending on level of ICS activation) reports to the Operations Section Chief or the Incident Commander and is responsible for the implementation of the Incident Action Plan that deals with the tactical control of the hazardous material. This includes safety, site control, research, entry and decontamination. The Hazmat Branch Director is responsible to safely and effectively manage the following tactical functions:  Establish and maintain control zones and access points into the hot zone and the warm zone.  Recommend public protection actions to the Operations Chief.  Monitor the site for the presence and concentration of hazardous materials.  Develop a site safety plan and conduct safety briefings for the Hazmat Branch.  Establish tactical objectives for the Hazmat Branch.  Ensure that safe operational procedures are followed including Chemical Protective Equipment, decontamination and leak and spill control procedures.  Coordinate hazmat tactical operations with Operations / Command to ensure that the Incident Action Plan is implemented. Version: March, 2018 Page | 24 Module 2: Safety HAZMAT SAFETY OFFICER Reports to the Incident Safety Officer as an Assistant Safety Officer. The Hazmat Safety Officer coordinates safety related activities relating to the Hazmat Branch and advises the Hazmat Branch Officer on all aspects of health and safety. Has the authority to stop or prevent unsafe acts and is responsible to:  Participate in the preparation and implementation of the Incident Tactical/safety plan.  Advise the Hazmat Branch Director of deviations from the plan or any dangerous situations.  Has the authority to alter, suspend, or terminate any unsafe activity.  Ensure the protection of Hazmat personnel from physical and chemical hazards.  Ensure the provision of emergency medical services for Hazmat personnel and coordinate with the Medical Team Leader. SITE CONTROL SUPERVISOR (Leader) Reports to the Hazmat Branch Director and is responsible for the establishment of the control zones and control of the movement of all people and equipment through designated access routes and the control of contaminants. Site Control Supervisor is responsible to:  Control access to the hazard site.  Establish and identify the Hot Zone (exclusion area) and the Warm Zone (control area).  Take appropriate action to prevent the spread of contamination.  Ensure that injured or exposed individuals are decontaminated prior to leaving the hazard area. Version: March, 2018 Page | 25 Module 2: Safety  Track the movement of people through the Hot and Warm Zone.  Observe and report any change in conditions external of the hazard area.  Coordinate with Medical Group (Sector) for proper separation and tracking of contaminated patients.  Communicate and coordinate with the Entry and Decon Supervisors. RESEARCH SUPERVISOR (Leader) Reports to the Hazmat Branch Director and provides technical information and advice relative to the chemical hazard. Identifies hazardous materials, collects and interpret information about the physical and chemical hazards to analyze the incident and develop the Tactical/Safety Plan. The Research Supervisor is responsible to:  Coordinate with the Planning Section Chief and assist with projecting potential harm.  Provide technical support to the Hazmat Branch Director.  Provide and interpret detection and monitoring information.  Provide analysis of hazardous material.  Determine the appropriate types of personnel  Protective equipment and decontamination.  Communicate and coordinate with the Entry and Decon Supervisors.  Provide technical information management with other agencies i.e., CHEMTREC, VDEM, Poison Control Center, chemical manufacturers. Version: March, 2018 Page | 26 Module 2: Safety ENTRY SUPERVISOR (Leader) Reports to the Hazmat Branch Director and is responsible for the overall entry operations in the Hot Zone including:  Supervise entry operations including backup teams.  Recommend tactical actions to mitigate the situation in the Hot Zone.  Carry out tactical assignments to perform rescue operations and mitigate the hazard.  Maintain control of the movement of people within the Hot Zone.  Communicate and coordinate with the Decon, Site Control and Research Supervisors. DECONTAMINATION (DECON) SUPERVISOR (Leader) Reports to the Hazmat Branch Director and is responsible for all decontamination functions, including:  Establish the Contamination Reduction Corridor(s), decon area.  Supervise the decontamination operations  Identify contaminated people and equipment.  Maintain control of the movement of people in the decon area.  Communicate and coordinate with the Entry, Site Control and Research Supervisors.  Coordinate the transfer of exposed patients, after decontamination, to the Medical Group.  Coordinate the handling, storage and transfer of contaminants within the decon area. Version: March, 2018 Page | 27 Module 2: Safety Hazardous Materials Branch/Group Organization HAZMAT Branch Director HAZMAT Safety Offier Site Control Reserach Entry Decontamination Supervisor/Leader Supervisor/Leader Supervisor/Leader Supervisor/Leader Monitoring HM Entry DECON Team Specialist Team 1 Team Control Technical Entry Medical Team Advisors Team 2 Team Entry Team 3 Reference Materials: Hazardous Materials – Managing the Incident, Noll and Hildebrand, Jones and Bartlett Learning, 4th edition, 2013. Hazardous Materials Regulations, Response, and Site Operations, Gantt, Delmar Publishing, 2nd edition, 2009. Hazardous Waste Operations and Emergency Response, Occupational Safety and Health Administration, 29 CFR 1910.120. Occupational Safety and Health Guidance Manual for Hazardous Waste Site Activities, NIOSH, OSHA, USCG, EPA, October 1985. Version: March, 2018 Page | 28 Module 2: Safety REVIEW QUESTIONS MODULE 2: SAFETY 1. Explain why the Incident Command System (ICS) is important during a hazardous materials incident. 2. Based on the brief summary of the HAZWOPER safety requirements, list the nine factors that will meet this requirement. 3. Why is it important to have a site safety and control plan? 4. What should preplan information include? 5. Hazard analysis identifies hazards and evaluates risks associated with the chemicals involved in an accident. What information should the analysis include? 6. What should be included for responders on a site map? 7. What should the Incident Commander include in the developing personnel assignments? Version: March, 2018 Page | 29 Module 2: Safety 8. What would the Incident Commander be looking for in identifying physical hazards and the degree of harm they present? 9. Why is hazard monitoring important in a Site Safety and Control Plan? 10. Why is a medical surveillance program important? Version: March, 2018 Page | 30 VDEM Hazardous Materials Technician Course Module 3: Chemistry Regulations and Standards OSHA 1910.120 (q) (6) (iii) Hazardous Material Technician Understand basic chemical and toxicological terminology and behavior. NFPA 472 Chapter 7 7.2.2.2 The HMT shall describe the following terms and explain their significance in the analysis process. (NOTE: this includes 54 terms.) The HMT shall demonstrate the following competencies:  Understand the physical properties of materials and how these affect the behavior of the material at an incident.  Identify and explain the chemical hazards of materials and what types and degree of harm they may cause.  Identify, select and apply tactical control methods used to safely and effectively reduce or limit the harm caused by hazardous materials. Version: March, 2018 Page | 31 Module 3: Chemistry INTRODUTION The Hazardous Materials Technician (HMT) must have a basic understanding of the physical properties, behavior and hazards of various substances. Knowing and understanding the very basics of chemistry is fundamental to being able to gather information and analyze the hazardous materials incident. This hazard analysis allows the HMT to make fundamental decisions regarding the development and implementation of safe and effective tactical operations. Properly analyzing the incident based on understanding the properties and hazards of the materials involved provides critical information so that the HazMat Technician is able to:  Determine actions to protect the public.  Establish control zones and safe operational areas.  Select detection and monitoring equipment and processes.  Select effective decontamination methods.  Select the proper chemical protective equipment.  Determine and implement safe and effective control tactics. PHYSICAL STATES OF MATTER A hazardous material can have three very different physical states. It may be a gas, a liquid, or a solid. The physical state a hazardous material takes plays a significant role in determining not only the measures that will be used to control a spill, but often the hazards that it presents.  Gas – Any substance that boils at atmospheric pressure at any temperature less than 80 F. DOT defines gases as materials with a boiling point below 680 F. Gases have no fixed volume or shape. They are extremely difficult to control and contain. In storage and transportation gases may be: o Compressed Gas – material when in a container has an absolute pressure of 40psi @ 70F or having an absolute pressure exceeding 104 psi at 130F or any liquid having a vapor pressure exceeding 40 psi at 100F. Version: March, 2018 Page | 32 Module 3: Chemistry o Liquefied Compressed Gas – gases that becomes a liquid in a container at normal temperature at pressure from 25 to 2,500 psi. o Cryogenic Gas – Liquefied gases with boiling points below -130 F.  Liquid –Liquids have a fixed volume but no fixed shape and will take on the shape of their container. Liquids at any temperature above their freezing point will release vapors.  Solid – Solids by definition are not mobile materials. They have a fixed volume and shape. However, when broken down into powder or dust form they can be transmitted by people, the atmosphere, or other carriers. Some solids are water- soluble and can become more hazardous when they come into contact with liquids or tissues. COMPOUNDS AND MIXTURES  Pure Substances – homogeneous material having a constant, fixed chemical composition with no impurities. They may be an element or a compound. Example: oxygen, chlorine, carbon monoxide, water  Element – simplest form of any substance cannot be decomposed into smaller units and remain that element. The smallest unit of an element is an atom. Example: hydrogen, carbon, oxygen, iron, fluorine  Compounds – a substance composed of two or more elements in chemical combination that has a fixed chemical composition. Example: methane (CH4), sodium chloride (NaCl), carbon dioxide (CO2)  Mixture – Materials that are made from two or more substances in varying proportions that are not chemically combined. These materials can be separated from each other by physical or chemical means (filtering, dissolving, evaporating, etc.) Example: air, gasoline, brass, wood o Solution – A uniformly dispersed mixture of one or more substances (solute) in one or more other substances (solvent). Example: liquid in liquid, alcohol-water, solid in liquid, salt-water, gas in liquid, carbon dioxide in water o Slurry –a pourable mixture of a solid and a liquid. Version: March, 2018 Page | 33 Module 3: Chemistry PHYSICAL PROPERTIES Boiling Point Boiling point is the temperature at which the transition from liquid to gaseous occurs. At this temperature, the vapor pressure of a liquid equals the surrounding atmospheric pressure so that the liquid rapidly becomes a vapor. Flammable materials with low boiling points generally present greater problems than those with high boiling points. For example, the boiling point of acetone is 133F (56C), and the boiling points for jet fuels range from 400F to 550F (204C to 228C). Melting Point The temperature at which a solid becomes a liquid. Materials with low melting points present problems because they melt faster and spread more easily. The reverse is also true, however. If the temperature of a liquid can be lowered, the technician may be able to convert it to a solid. Sublimation When a substance passes directly from a solid state to a vapor state without passing through a liquid state, for example, naphthalene used in mothballs. An increase in temperature increases the rate of sublimation. During an incident, the hazardous materials technician should assess the toxicity and flammability of the vapors of any material that sublimes. Vapor Pressure Vapor pressure is the pressure exerted on the inside of a closed container by the vapor in the space above the liquid in the container. Products with high vapor pressures have a greater potential to breach their containers when heated, since the pressure increases as the temperature rises. Products with high vapor pressures are more volatile. Vapor pressure is measured in a variety of ways.  Millimeters or inches of mercury – mm Hg / in Hg  Pounds per square inch (absolute) – psia  Atmosphere (atm) 760 mm Hg = 14.7 psia = 1 atmosphere (at sea level) Version: March, 2018 Page | 34 Module 3: Chemistry Examples of vapor pressure in common materials Material Vapor Pressure (Vp) – mm/Hg Water 21 Acetone (Propanone) 100 Chlorine 4,800 Critical Temperature and Pressure Critical temperature and pressure relate to the process of liquefying gases. The critical temperature is the minimum temperature required to liquefy a gas, no matter how much pressure is applied. The critical pressure is the pressure that must be applied to bring a gas to its liquid state. A gas cannot be liquefied above its critical temperature. The lower the critical temperature, the less pressure is required to bring a gas to its liquid state. If a liquefied gas container exceeds its critical temperature, the liquid will convert instantaneously to gas, which may cause the container to fail violently. Expansion Ratio The expansion ratio is the amount of gas produced by a given volume of liquid at a given temperature. For instance, liquid propane has an expansion ratio of liquid to gas of 270 to 1, while liquefied natural gas has an expansion ratio of 635 to 1. Obviously, the greater the expansion rate, the more gas is produced, and the larger the endangered area becomes. Vapor Density Vapor density is the relative density of a vapor compared to air. The vapor density of air is 1.0. If a material has a vapor density higher than 1.0, it is heavier than air and will settle. Toluene, for example, has a vapor density of 3.14, and will settle and pool in low- lying areas. If a vapor density is less than 1.0, it is lighter than air and will rise and tend to dissipate. Version: March, 2018 Page | 35 Module 3: Chemistry Specific Gravity Specific gravity is the weight of a solid or liquid compared to an equal volume of water. If a material has a specific gravity greater than 1.0 and it does not dissolve in water, it will sink. If its specific gravity is less than 1.0, it will float on water. This becomes important when conducting some types of damming or booming operations and when dealing with flammable liquids. #2 Heating Oil Carbon tetrachloride SG – 0.84 SG – 1.59 Solubility The ability of a substance to form a solution with water can be important when determining control methods. For example, gasoline is insoluble, while anhydrous ammonia is soluble. Solubility is expressed as:  Negligible: less than 0.1%  Slight: 0.1 to 1.0%  Moderate: 1 to 10%  Appreciable: More than 10% Miscibility The term miscible refers to the tendency or ability of two or more liquids to form a uniform blend, or to dissolve in each other. Liquids may be totally miscible, partially miscible, or not at all miscible  Miscible: will mix  Immiscible: will not mix Version: March, 2018 Page | 36 Module 3: Chemistry Persistence A material’s ability to remain in the environment chemically unchanged. The more persistent a material is, the greater the propensity for it to remain harmful over a period of time. Temperature of Product The temperature of a product will influence the measures taken to control an incident that involves that product. A product’s temperature may also present hazards. An incident involving molten sulfur, for example, raises a different set of concerns than one involving a cryogenic material such as liquefied natural gas. Viscosity A measure of the thickness of a liquid, determines how easily it flows. Liquids with high viscosity, such as heavy oils, must be heated to increase their fluidity. Liquids that are more viscous tend to flow more slowly, while those that are less viscous will spread more easily. During an incident, liquids that are less viscous are likely to flow away from a leaking container, expanding the endangered area. Volatility Volatility describes the ease with which a liquid can pass into the vapor state. The higher a material’s volatility, the greater its evaporation rate. Vapor pressure is a measure of a liquid’s propensity to evaporate. Thus, the higher a liquid’s vapor pressure, the more volatile it is. During an incident, a volatile material will disperse in air and expand the endangered area. CHEMISTRY Chemistry has two basic subdivisions: organic and inorganic. Organic chemistry is based on substances that contain carbon. Organic materials are derived from materials that are or once were living. Organic compounds contain chains of two or more carbon atoms. An example of an organic compound is propane. Organic materials are significant to the technician, as the majority of them are known to be flammable and many are also toxic. The chemistry of nitrogen, oxygen and other non-carbon materials is the content of inorganic chemistry. Inorganic materials may still contain carbon. However, they lack the characteristic carbon chains found in organic materials. Examples of an inorganic material are nitric acid, sodium bicarbonate and carbon dioxide. Version: March, 2018 Page | 37 Module 3: Chemistry Atomic Structure All matter (substances) is made of atoms.  Atoms are the building blocks of matter. Atoms are composed of three basic units:  Protons – Particles that are found in the center, or nucleus, of the atom having a positive charge.  Neutrons – Particles found in the nucleus, have no charge.  Electrons - Particles found in the space surrounding the nucleus, they have a negative charge. These spaces are called the electron shells. The particles that make up an atom have mass and an electrical charge: Mass Particle Charge Location (Atomic Mass Units) Proton +1 1 AMU Nucleus Neutron 0 1 AMU Nucleus Electron -1 1/2000 AMU Space around nucleus Version: March, 2018 Page | 38 Module 3: Chemistry Almost all of the mass of the atom is in the nucleus. The electrons are what take part in chemical bonding and reactions. Atoms like to try and fill their electron shells. Depending on the number of electrons associate with an atom, there can be many electron shells. The number of protons and electrons are normally equal in a stable atom. ELEMENT An element is a substance of similar atoms with the same atomic number (number of protons). Elements cannot be broken down further by chemical means. An element’s chemical properties are determined by the number of protons in the nucleus and the corresponding number of electrons around the nucleus. There are 118 named elements. Of those, 92 are found in nature. The remaining elements are synthetically made in the laboratory. Isotopes - The atoms of an element all have the same number of protons. However, variations in the atomic mass of the atoms can occur. When this occurs, the number of protons stays the same but the number of neutrons changes. When this occurs, the new atom is said to be an isotope of the original atom or element.  Some isotopes are very unstable. As they break down, they release particles and energy. This breakdown is called radioactivity and the particles and energy released are called radiation. Ion – An atom or radical that has lost or gained an electron, therefore has acquired an electric charge.  Loss of electron = positive charged atom called a cation  Gain of electron = negative charged atom called an anion Allotrope – The existence of a substance in two or more forms with different physical and chemical properties. Example: Carbon existing as a diamond, graphite and carbon black Version: March, 2018 Page | 39 Module 3: Chemistry Types of Elements Metal – an element that conducts heat and electricity well has a high physical strength and is ductile and malleable. Metals are to the left of the stair step line on the periodic table. Many metals are extremely toxic. Nonmetal – an element that does not conduct heat and electricity, has low physical strength and is neither ductile nor malleable. Nonmetals are to the right of the stair step line on the periodic table. Metalloid – an element that exhibits general physical properties of both metals and nonmetals. PERIODIC TABLE The periodic table is an organized chart that contains all elements that are known to exist. The table is arranged in ascending order by the element’s atomic number. From the table, one can obtain valuable information on elements. Atomic Number The atomic number of an element is the number of protons in its nucleus. Atomic Mass The atomic mass is determined by adding together the number of protons and the number of neutrons. It is usually displayed as a decimal number on a Periodic Table. Atomic mass is useful for determining relative density of a material and for calculating quantities of reactants for neutralization reactions. Periods -horizontal rows In a given period, the properties of the elements gradually pass from a chemically active metal to a chemically active nonmetal nature, with the last element in the period being an inert gas. Groups - vertical columns The group number indicates the number of electrons in the outer shell of the atom. It is significant because it helps describe the reactivity of an element. Atoms will react in such a way as to complete their outer shell; i.e., two electrons in the first shell and eight electrons in the outer shells. This filling of the outer-most shell is called the Octet Law. Elements with similar properties are classed together in groups or families. There are four families of significance the Technician needs to recognize. Version: March, 2018 Page | 40 Module 3: Chemistry Group 1 - The alkali family. The elements in this family are Hydrogen, Lithium, Sodium, Potassium, Rubidium, Cesium, and Francium. Each has one electron in its outer shell and has properties similar to the others. All of the elements except for hydrogen will explode on contact with water and are Pyrophoric. Group 2 - The alkali earth family. Examples include Magnesium, Calcium, and Radium. These elements have two electrons in their outer shell. These metals are also chemically reactive, but not as reactive as Group IA. They will decompose in water, and may be explosive and ignite in air, but only after being exposed to a heat source. Group 17 - The halogen family. Examples are Fluorine, Chlorine, and Bromine. These elements have seven electrons in their outer shells. They are exceptionally reactive nonmetals, and, like oxygen, are oxidizers. In fact, Fluorine is a stronger oxidizer than oxygen. Group 18 - The Noble Gas family. Most of these gases exist as a major part of the atmosphere. These gases are non-reactive. Version: March, 2018 Page | 41 Module 3: Chemistry NON-METALS METALS Version: March, 2018 Page | 42 Module 3: Chemistry Chemical Properties and Behavior Chemical properties of a material are those changes that the material is capable of undergoing due to reactions of materials at the atomic level. Chemical properties affect how atoms interact with each other and the formation of other compounds. Chemical Reactions A chemical change which occurs when two or more substances react with each other and produce a different substance or energy is applied to a substance and a different substance is produced. In a chemical reaction energy is either absorbed or liberated. The chemical reaction of materials in a container may result in a build-up of heat, an increase in pressure, a corrosive product, or a material that may react if shocked (heat, mechanical, or chemical). Under these conditions the container may fail. Ionic Bonding - A chemical reaction that combines metal elements with nonmetal elements producing a compound called a salt. This type of bonding produced products that are held together by the differential electrical charge between the parts (or ions). An example is table salt (sodium chloride). Covalent Bonding – A chemical reaction that combines two non-metals together. The product is a non-salt. This type of bonding produces products that are held together by the sharing of electrons between the parts. An example is methane. Developing the Chemical Hazard Profile for Incident Analysis In order to understand the behaviors and hazards of the material(s) involve the HMT should research the physical properties and chemical hazards of the substance(s), and develop a profile of the chemical hazards. Developing this Hazard Profile includes;  Identifying the hazard class,  Evaluating the potential for energy to be release and chemical reactivity  Determine the physical state based on boiling point or melting point.  Evaluating the fire hazards.  Evaluating the health hazards. Version: March, 2018 Page | 43 Module 3: Chemistry The HMT must be concerned about the potential of energy being released which may travel very rapidly and significant distances to cause harm. Mechanical, radiation, thermal and chemical energy may be released from the hazard area and be a greater hazard than direct contact with the material(s) involve in the incident. Therefore, the HMT should evaluate the energy being released or the potential for energy release as a primary hazard of the incident.In order to accomplish this the HMT should evaluate the material(s) involved and the incident conditions to identify if the material is:  Explosive - Hazard Class 1  Reactive with other chemicals including water and air – Hazard Class 4, 5, 8  Polymerization hazard – Hazard Class 2 and 3  Chemically unstable  Radioactive – Hazard Class 7 Chemical Reactivity Hazards Chemical Reactivity Chemical reactivity describes a substance’s ability to release energy or undergo change. Examples of reactivity include self-reactive, water-reactive, or air-reactive materials, polymerizing materials, corrosives, explosives, or radioactive materials. Unstable Materials Substances that decompose spontaneously, polymerizes or otherwise self-reacts in a hazardous manner. Oxidation Potential The ability of a material to spontaneously react with oxygen from the air or from a chemical oxidizer at room temperature without any outside heat being applied. Explosive Materials Explosive means any substance or article, including a device, that is designed to function by explosion (i.e., an extremely rapid release of gas and heat) or that, by chemical reaction within itself, is able to function in a similar manner even if not designed to function by explosion. Version: March, 2018 Page | 44 Module 3: Chemistry  Detonation - A sudden, violent release of mechanical, chemical, or nuclear energy from a confined region; a detonation is propagated by a shock wave and travels at supersonic speed.  Deflagration - To burn very, very rapidly; the speed of reaction is much faster than ordinary combustion but travels much slower than a detonation. Possible hazards: Explosive; exposure to heat, shock or contamination could result in thermal and mechanical hazards. Chemically Reactive Materials Instability Materials that decompose spontaneously, polymerize, or otherwise self-react are generally considered unstable. They do not need to mix with other chemicals to react. The term instability is often used interchangeably with the term reactivity. Water reactive Materials that when in contact with water will produce flammable or toxic gases, or exothermic reactions or decompose. For example, most alkali metals will react violently when they come in contact with water. Those metals are so reactive that they do not exist as metals in nature. The outer electron shell of the alkali metals is unstable, and therefore reacts rapidly and strongly with the oxygen molecules in water. Examples of water reactive materials and their by-products.  Sodium Metal – Hydrogen and Sodium hydroxide  Calcium Carbide - Acetylene and Calcium hydroxide  Sodium Hydride - Hydrogen and Sodium hydroxide Pyrophoric Materials (Air Reactive) Pyrophoric materials are those materials that react spontaneously with air. Many scientists and producers of these materials attempt to make a distinction between a pyrophoric material reacting in clean, dry air, or those that react in moist air. (Note - When a pyrophoric material reacts in moist air, it is because of the water content causing the reaction, therefore making it water reactive.) Characteristics - Some of these materials may burst into flames; some may decompose slightly less violently into noxious components while others may detonate. Version: March, 2018 Page | 45 Module 3: Chemistry Example: Phosphorus - White phosphorus will spontaneously ignite when exposed to air. Polymerization Polymerization is a chemical reaction in which small molecules combine to form larger molecules. The polymerization process release large amounts of energy that may damage the container.  Monomers – The small molecules that are the base unit for the polymerization process. An example is styrene.  Polymer – Large molecules formed from smaller sub-units or monomers. An example is polystyrene.  Inhibitor – An inhibitor is a chemical that is added to a monomer to prevent the chemical reaction. If the inhibitor is released during an incident, an uncontrolled polymerization process can take place that may damage the container.  Catalyst – A catalyst is used to speed up the rate of a chemical reaction. If not used properly, a catalyst can initiate an uncontrolled polymerization process. Catalysts do not enter into the chemical reaction (do not chemically change). Examples of Reactive Materials Chemical Instability Water Reactive Pyrophoric Polymerization Butyraldehyde Metal salts White phosphorus Acrylonitrile Organic peroxides Acids Uranium Propylene Azides Bases Triethylaluminum Vinyl chloride Fulminates Group I elements di-Ethyl zinc Styrene Nitrate esters Iron sulfide Oxidizers Any substance that may enhance or support combustion of other materials generally by yielding oxygen; a substance that will readily reacts to, promotes or initiates combustion such as the halogens; under certain circumstances may undergo vigorous self-sustained decomposition due to contamination or heat exposure. These materials can be in gas, liquid or solid state. They readily and easily release the oxygen atoms in the compound or are a halogen. Fluorine is a more powerful oxidizer than oxygen. Oxidizers can be toxic, very sensitive to energy (heat, pressure or shock). Version: March, 2018 Page | 46 Module 3: Chemistry  Inorganic Compounds that are Oxidizers There are certain ionic compounds that will readily release oxygen. The basic formula for these oxidizers is: Metal + Non-metal + Oxygen Examples  Sodium hypochlorite NaClO  Sodium nitrate Na2NO3  Peroxides Any compound containing a bivalent Oxygen group, peroxide ion, O-O (2 oxygen atoms) they release oxygen readily and are strong oxidizers. Peroxides are a group of hazardous materials that are man-made, not normally occurring in nature due to their inherent instability and reactivity. Their use is mainly to initiate or catalyze a polymerization reaction.  Inorganic peroxides Compounds that have hydrogen or any metal ionically bonded to a peroxide ion. Example: Hydrogen Peroxide, H-O-O-H Some inorganic peroxides are strong oxidizers, toxic, and when they come in contact with a combustible material, may burst instantly into flames.  Organic peroxides Organic compounds that contain the peroxide ion. They are extremely unstable and the slightest amount of energy may be enough to cause a rapid decomposition with the release of high amounts of energy. Organic peroxides are kept at low temperatures to prevent these bonds from disintegration, which will release energy. Version: March, 2018 Page | 47 Module 3: Chemistry  Self-Accelerating Decomposition Temperature – The SADT is a property of every peroxide. The typical range of SADTs is between 0F and 50F. Regardless of the temperature, if some portion of the material reaches it, decomposition will begin. Once this decomposition begins, there is no way to stop it.  Maximum Safe Storage Temperature – The highest temperature at which to safely store organic peroxides. When an organic peroxide reaches a temperature above the MSST, the material will decompose and may explode.  Activators - When oxidizers come in contact with either an energy or a chemical activator, they may decompose rapidly causing the release of vast quantities of oxygen and possibly heat. This breakdown may accelerate the fire of a nearby combustible material. Since many oxidizers are metals, toxic gases may be released as well. Energy activators - There are two types of energy activators. The primary activator is heat and the secondary is pressure. Heat can be produced either from an outside source, or as the material is decomposing. Pressure is produced if the material is contained in a storage vessel. If the material is decomposing, oxygen is being released and heat is being produced. While this is happening, pressure is being built up to the point of container failure. Chemical activators - These materials have the ability to react with oxygen from air or some type of oxidizer at normal temperature with no outside heat source being applied. These materials will chemically react with metals and some non-metals to begin the process of releasing oxygen and heat, causing a hypergolic reaction. Radioactive Materials Radioactive Material A material containing an isotope that spontaneously emits ionizing radiation. Radioactivity The emission of radiation from an atom due to artificial or natural nuclear breakdown. Version: March, 2018 Page | 48 Module 3: Chemistry Radioisotope (Radionuclide) An isotopic form of an element (either natural of artificial) that exhibits radioactivity. Radiation The movement of energy through space or matter in the form of waves or particles.  Non-Ionizing radiation – This type of radiation causes atoms and their bonds to vibrate. This vibration causes friction with the release of heat. Examples of this type of radiation include visible light, infrared energy, microwaves, and radio waves.  Ionizing radiation – This type of radiation causes changes in the atomic structure of the atom. These changes include the ejection of atomic particles and the release of energy from the atom. Alpha particles – Alpha particles are made up of 2 protons and 2 neutrons (a helium nucleus). They are fairly large, slow-moving particles. They travel only a few centimeters in air. Alpha particles present an internal hazard. Paper or Tyvek can stop alpha particles. Beta particles – Beta particles are composed of electrons that are ejected from the atom. They are smaller and faster than alpha particles. Beta particles can travel several meters in air. Beta particles present both internal and external hazards. A thick book can stop beta particles. Neutron particles – Neutron particles are ejected from the nucleus during radioactive decay. These particles are usually associated with nuclear fission (an atomic bomb detonation or around nuclear reactors). These particles can travel great distances because they have a neutral charge. They present an internal hazard to living tissue. X-rays – X-rays are produced when the electrons in an atom move between electron shells. It is considered high-energy radiation that presents both an external and internal hazard. Gamma rays – Gamma rays are similar to X-rays but of greater energy. The main difference between X-rays and Gamma rays is that gamma rays originate in the nucleus of the atom and usually follow alpha or beta decay. Gamma rays present both external and internal hazards. Several cm of concrete or lead is required to stop gamma radiation. Version: March, 2018 Page | 49 Module 3: Chemistry THE PENETRATING EFFECTS OF RADIATION Measuring Radioactivity  Curie – (Ci) Unit used to measure radioactivity. 1Ci = 37 billion disintegrations per second (dps).  Becquerel – (Bq) Metric unit of measure for radioactivity. 1 Bq = 1 disintegration per second (dps).  Specific Activity – The activity of a radioactive source per mass. Generally measured in curies per gram (Ci/g).  Radioactive Half-Life – The time it takes for an unstable element to lose one- half of its radioactivity. Version: March, 2018 Page | 50 Module 3: Chemistry  Roentgen (R) The amount of gamma radiation that will cause about two billion ion pairs in one cm3 of dry air. It is a measure of the ionizations of the molecules in a mass of air. Note: most instruments are read in Roentgens or Roentgens per hour.  Radiation Absorbed Dose (rad) Relates to the amount of energy actually absorbed in some materials. Equals the energy absorption of 100 ergs per gram of irradiated material (an erg is a measure of work).  Radiation Equivalent Man (rem) REM measures the radiation effect on the body. Both the dosage of radiation and the potential for harmful effects are taken into account. For emergency response operations, R – rad – rem are roughly equivalent for gamma radiation. Radioactive Material Labels There is certain information that is required to be displayed on radioactive material labels. This includes:  Vertical bars - Depending on the level of radiation emitted from the package, radioactive materials will bear one of three types of labels: Radioactive White-I, Radioactive Yellow-II, or Radioactive Yellow-III. Radioactive White-I (1 bar) identifies contents that have the lowest level of external radiation hazard, and Version: March, 2018 Page | 51 Module 3: Chemistry Radioactive Yellow-III (3 bars) the highest level. These labels do not indicate the amount of internal hazard that the package may contain.  Contents, Activity and Transportation Index - This information is displayed on the label. The transport index (TI) indicates the radiation dose rate (in millirems per hour) measured at one meter (3.3 feet) from the surface of the package. It indicates the degree of control required by the shipper and determines the number of such packages that are allowed in a vehicle or storage area. The TI is only displayed on Yellow II and Yellow III labels. The label also indicates the contents and activity. Corrosive Materials Any substance that causes the destruction of living tissue by chemical reaction. DOT Regulation – a liquid or solid that causes destruction of human tissue or a liquid that chemically reacts with steel or aluminum. pH – a numerical scale from 0 to 14 used to quantify the acidity or alkalinity of an aqueous solution with neutrality indicated as 7. Acid – a corrosive with a pH of less than 7, a compound that forms hydrogen ions when dissolved in water Base (Alkaline) – a corrosive with a pH of more than 7. Version: March, 2018 Page | 52 Module 3: Chemistry Acids Compounds that, when dissolved in water, will yield hydrogen ions. They are grouped into two broad classifications: organic and inorganic. Organic acids - contain carbon. Organic acids are similar in their molecular structure and contain a grouping of atoms called a carboxyl group. These tend to be weak acids and the symbol is abbreviated as COOH, which is combined with other hydrogen and carbon atoms in a chain or ring. Organic acids can be flammable due to the carbon content. Organics may be explosive and very toxic. Example: Acetic Acid - CH3COOH, Formic Acid - HCOOH Inorganic acids - do not contain carbon. They are sometimes referred to as mineral acids and are not flammable. However, these acids often act as an oxidizing agent that can ignite other combustible materials in a spill. They are also water reactive. Examples: Hydrochloric Acid – HCl, Sulfuric Acid - H2SO4 REMEMBER Add Acid to Water, NOT Water to Acid! Hazards of acids (organic and inorganic)  Corrosive  Oxidizer  Explosive  Flammable  Polymerization  Reactive  Water reactive  Unstable  Toxic Bases (also referred to as Alkali or Caustic) Substances that liberate hydroxide anions when dissolved in water. Bases react with acids to form salts and water. Bases have a pH greater than 7 and turn litmus paper blue, have a bitter taste and a slippery feel in solution. Bases have the same general property as acids in that they also can damage human tissue and materials, often more than acids. Version: March, 2018 Page | 53 Module 3: Chemistry Example: Sodium Hydroxide (lye) - NaOH, Potassium Hydroxide (caustic potash) - KOH Measurement Flammable Gases, Liquids and Solids In fire, the process of oxidation is occurring very quickly while heat and light are released. If the process of oxidation is much faster than in a fire, or the amount of energy released is increased, an explosion occurs. Simply put, if we look at the common, everyday fire, matter (fuel) is reacting with the liberation of energy (heat and light). Flammable products can either be solid, liquid or gas. Each state has characteristic physical properties that enable responders to anticipate behavior. Earlier we talked about fire being a chemical process. This, we all know, is composed of heat, fuel, and oxygen. All these can be present at the same time, but if conditions are not right, then fire will not occur. In order for a substance to burn, it will need some other things to be present. Flash Point Flash point in the minimum temperature to which a material must be raised to allow for combustion in the presence of an ignition source. The flash point is indicative of vapor flash across the surface of a liquid. Fire point - In order for sustained combustion to occur the fire point must be reached. The fire point is usually 1-3F above the flash point. Version: March, 2018 Page | 54 Module 3: Chemistry Flammable Range Flammable range is the percentage of vapor in the air, in which ignition will occur. Flammable range is described in terms of Lower and Upper Flammable Limits, also known as Lower and Upper Explosive Limits or LEL and UEL.  If the vapor/air mixture is less than the LEL, the mixture is too lean.  If the vapor/air mixture is greater than the UEL, the mixture is too rich. 0% % LEL 100% THIS IS WHAT IS TYPICALLY MEASUED BY RESPONDERS Too little fuel Too much fuel Flammable Range (LEAN) (RICH) Oxygen in Atmosphere (20.9%) LEL UEL 0% 5% 15% 30% Percent by Volume (in air) Remember LEL and UEL can go from too lean to just right, or from too rich to just right by the technician entering the atmosphere. Ignition Temperature (Also referred to as Auto Ignition Temperature) The minimum temperature which a material must be heated in order to initiate self- sustained combustion. While the flash point of a material is a function of physical characteristics, i.e. vapor production, ignition temperature is a chemical change in the material. Molecular bonds in the material are broken and become subject to oxidation. When this oxidation becomes rapid, and heat and light are produced, fire is the result. Larger, heavier molecules will typically have lower ignition temperature than light, small chemicals. Animal/vegetable oils have low ignition temperatures and will undergo spontaneous ignition if confined. Version: March, 2018 Page | 55 Module 3: Chemistry Example: Gasoline (87 Octane) FP = -36F IT = 853F Diesel FP = 100 IT = 494F Products of Combustion All productions of combustion, from cigarette smoke to the smoke from a fire involving pesticides, have some toxic effects. Some materials generate more highly toxic products of combustion than others, and appropriate levels of protective clothing and equipment must be used to counter them. Hydrocarbons and Hydrocarbon Derivatives Crude oil pumped from the ground is a mixture of many molecules. It is refined into many usable products by a process called fractional distillation. In this process the molecules are separated, collected at different levels of a fractionating tower and sent away to be blended into many familiar products we use (for example, gasoline, kerosene, asphalt, fuel oils and many other liquid petroleum products). Hydrocarbons are made up of carbon and hydrogen that are covalently bonded to each other. Note- All organic compounds are carbon based. Organic compounds are derived from living materials and materials that lived in the past, such as plants or decayed products. The carbon atoms can link together through covalent bonding to form long chains that contain hundreds of atoms. Hydrocarbon Families Hydrocarbons are broken down into several families with derivatives in each family. For this course, we will discuss each family and give the characteristics of each. The families are: Saturated, Unsaturated, Aromatic, and Halogenated. Saturated hydrocarbons These molecules are saturated with hydrogen atoms. The molecules contain twice as many hydrogen atoms, plus two, as they do carbon atoms, and each bond is a single covalent bond. Most saturated hydrocarbons are heavy, and, with the exception of methane, have a vapor density greater than 1.0. The technical family name for this type of hydrocarbon is the Alkanes. Example: Propane C3H8 3 Carbons + 6 Hydrogens + 2 Hydrogens Version: March, 2018 Page | 56 Module 3: Chemistry Alkanes are about 60% of all the petroleum oil and are referred to as petroleum hydrocarbons, or paraffin hydrocarbons. Alkanes are not very reactive and do not react with strong acids or bases. However, they are able to be oxidized and will burn. Alkane names will end in -ane. Examples of alkane vapor density: Methane 0.6 Ethane 1.0 Propane 1.6 Butane 2.0 Hexane 3.0 Unsaturated hydrocarbons The reason some hydrocarbons are called unsaturated is because they do not contain as many hydrogens per carbon atom as the saturated hydrocarbons. Unsaturated hydrocarbons contain multiple bonds between the carbons somewhere in the molecular structure. These multiple bonds, coupled with the relatively low hydrogen content, are the reason this type of hydrocarbon is highly reactive. All are considered toxic. The family groups that make up unsaturated hydrocarbons are Alkenes and Alkynes. Alkenes - Most alkene compound names end with -ene. Alkenes are made up of carbons that attach to each other with double covalent bonds. Because of these bonds, alkenes are very reactive. The most frequently encountered alkenes are ethylene and propylene. Formula for alkenes is CnH2n. -yne – Alkynes are made up of carbons that attach to each other with triple covalent bonds. These bonds are highly unstable. Alkynes generally do not exist in nature due to their reactivity. The most common alkyne is acetylene or ethyne. The empirical formula for alkynes is CnH2n-2. When alkenes and alkynes come in contact with an oxidizer, a very rapid and intense fire will occur. This is called a hypergolic reaction. Version: March, 2018 Page | 57 Module 3: Chemistry Aromatic Hydrocarbons They are called “aromatic” because of the very sweet and pleasant odors they emit. Aromatics contain the lowest hydrogen content of all the hydrocarbon families. The aromatics are found in petroleum oil with the saturated hydrocarbons. Since they are found in petroleum, they are referred to sometimes as coal tar hydrocarbons because they are unreactive and naturally occurring. However, aromatics are flammable and are known carcinogens. Structure - Aromatic hydrocarbons are structured very differently than the other hydrocarbon families. Aromatics are referred to as ringed hydrocarbons. Benzene is the parent aromatic hydrocarbon. Examples of Hydrocarbon Families Halogenated Family Saturated Unsaturated Aromatic HC H H H H H H H C H H Cl C C Structure H C C C H C C H C C H C C C C H H H H H H C H H H H Name Propane Ethene Ethyne/Acetylene Benzene Vinyl chloride Formula C3H8 C2H4 C2H2 C6H6 C2H3Cl Type Alkane Alkene Alkyne Resonant Alkyl halide Halogenated hydrocarbons These are hydrocarbons in which a hydrogen atom is replaced with a halogen atom. Since all halogens of Group VIIA react similarly, and the number of hydrocarbons is so large, there are a very high number of potential halogenated hydrocarbons. Halogenated hydrocarbons include flammable and combustible liquids, liquids that may not ignite, urethane foams, and fire extinguishing agents. Their materials are toxic. Example: Methyl Chloride – CH3Cl Flammable (Combustible) Solids In addition to ordinary combustibles (Class A fuel such as wood, paper, cotton wool), there are solid materials that present a significant fire hazard. There are two major types of flammable solids; combustible elements and combustible metals. Version: March, 2018 Page | 58 Module 3: Chemistry Carbon, phosphorus and sulfur are elements that can burn in addition to having other hazardous characteristics. Carbon in the form of coal is combustible and in bulk storage may burn so hot that is will break down water to release hydrogen and oxygen. There are two allotropes of Phosphorus that are combustible and hazardous. White phosphorus is unstable at room temperature, has an auto ignition point of 86 F and will spontaneously ignite in dry air. Red phosphorus sublimates at 781F and ignites at 500F. Sulphur melts at 248F and ignites at 450F. When sulfur burns the products of combustion are toxic. Combustible metals present multiple hazards in addition to burning. The alkali metals such as lithium, sodium and potassium are combustible, water reactive and the products of combustion are toxic. Other metals such as magnesium, aluminum, titanium and zirconium will burn and are especially dangerous in powder or dust form as they can ignite with explosive force. Because these materials burn at very high temperatures water and CO2 are not effective extinguishing agents and can break down to release oxygen. There are certain metallic compounds that are combustible such as the metallic phosphides and metallic carbides. These compounds may also have multiple hazards such as being toxic and water reactive. Toxic and Poisonous Materials All hazardous materials can be toxic in some form. However, there are some chemicals that in small quantities can be extremely hazardous to a person’s health: “A poison or toxin is a chemical in relatively small amounts that has the ability to produce injury, by chemical action, where it comes in contact with susceptible tissue (i.e., target organs).” Effects Local Effect - Local effects result in injury to a localized area on the skin, face, or limbs. It also can affect the throat, lungs, and the digestive tract. Systemic Effect - Occurs when the toxicant enters the bloodstream and will damage many tissues in the body. Version: March, 2018 Page | 59 Module 3: Chemistry Types of Toxic Materials Poisons - Substances that are toxic at low levels. Irritants - Substances that cause local inflammatory reaction upon contact. Asphyxiants - Substances that interfere with the oxygenation of tissue. Simple Asphyxiants – These materials displace the oxygen in the atmosphere so that oxygen does not enter the lungs or bloodstream. Chemical Asphyxiants – These materials chemically bond with the hemoglobin in blood and prevent the blood from bonding to red blood cells or from releasing to the cells. Carcinogens - Substances that cause cancer in tissue. Biological Agents – Biological agents include bacteria, viruses, microorganisms and their toxins. Blood Agents – Chemical compounds containing the cyanide group that prevents the body from utilizing oxygen. Nerve Agents – Organophosphates that disrupt the mechanism by which nerves transfer messages to organs. Vesicants (Blister Agents) - chemicals that cause blistering and burning of tissue upon contact. Riot Control Agents – chemicals that are irritants. Version: March, 2018 Page | 60 Module 3: Chemistry Types of toxic materials Name Definition Major Sub-Groups Action Examples  Pesticides  Nephrotoxin  Targets kidneys  Cyanide  Hematotoxin  Targets blood  Arsine A substance that is toxic at (Blood agent) Poisons  Sarin extremely low levels  Neurotoxin  Targets nervous  Phosphine System  Hepatotoxin  Targets liver  Carbon dioxide  Simple  Displaces oxygen in (simple) A substance that interferes atmosphere  Nitrogen Asphyxiants with the oxygenation of  Chemical  Prevents oxygen (simple)

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