Hazmat Operations cheat sheet

NFPA 704 quadrant order: blue = health, red = flammability, yellow = instability, white = special hazards (OX, W with slash, SA).

DOT hazard classes 1-9: 1 explosives, 2 gases, 3 flammable/combustible liquids, 4 flammable solids/spontaneously combustible/dangerous when wet, 5 oxidizers/organic peroxides, 6 toxic/infectious, 7 radioactive, 8 corrosive, 9 miscellaneous.

UN hazard identification number (Kemler) first digit 2 = gas, 3 = flammable liquid, 4 = flammable solid, 5 = oxidizing, 6 = toxic, 7 = radioactive, 8 = corrosive; doubled digit = intensification, X prefix = reacts with water.

Placards are required for bulk packages (generally >119 gallons liquid or >882 lb gross for solids) and for any quantity of Table 1 materials.

Seven clues to hazard identification: occupancy/location, container shape, markings/labels/placards, shipping papers, facility documents, senses, and human behavior.

Shipping paper order for hazardous materials: proper shipping name, hazard class/division, UN/NA identification number, and packing group.

Pipeline markers give commodity name, operator, and emergency phone; they do not give pressure, flow, or volume.

Cryogenic liquids produce visible frost/fog and expand roughly 700-1000 times their liquid volume when vaporized; oxygen-deficient atmospheres below 19.5% O2 are IDLH-adjacent.

Risk = probability of an event x severity of consequences; risk assessment precedes selection of tactical objectives.

IDLH is the maximum airborne concentration from which a worker could escape within 30 minutes without irreversible health effects.

ERPG-2 is the maximum concentration below which nearly all persons could be exposed for up to 1 hour without irreversible or serious health effects.

TLV-TWA is an 8-hour time-weighted average; TLV-STEL is a 15-minute excursion; TLV-C is a ceiling that must never be exceeded.

Lower flammability limit (LFL) is the minimum vapor concentration that will burn; below LFL the mixture is too lean, above UFL too rich.

Vapor density >1 sinks and collects in low areas; <1 rises. Vapor pressure rises with temperature, increasing off-gassing and downwind hazard.

Specific gravity >1 sinks in water; <1 floats. Water-soluble materials disperse in water; insoluble materials form a separate phase.

AEGL tiers: AEGL-1 discomfort, AEGL-2 serious long-lasting effects, AEGL-3 life-threatening; used for public protective action decisions.

Isolation distances scale with container size and fire involvement; a fire impinging on a container requires the largest initial isolation and evacuation distances.

Initial notifications: fire/EMS dispatch, CHEMTREC (1-800-424-9300) or CANUTEC (1-888-226-8832), state/provincial environmental agency, and the National Response Center (1-800-424-8802) for releases meeting reportable quantities.

CERCLA reportable quantity triggers a release notification to the National Response Center; the RQ is listed per substance (e.g., 1 lb, 10 lb, 100 lb, 1000 lb).

Calls to CHEMTREC should include: caller name and callback, location, material name, quantity, container type, injuries, and current conditions.

ICS span of control is 3-7 subordinates per supervisor, with 5 as the target.

Incident Command System sections: Operations (tactical), Planning (situation/action plan), Logistics (resources), Finance/Administration (cost).

The Incident Action Plan is produced in the Planning Section and covers one operational period; the Safety Officer has authority to halt unsafe operations.

Clear text (plain language) is used for radio communication; no ten-codes or agency-specific codes during multi-agency incidents.

The emergency response guidebook's initial isolation and protective action distances apply for the first 30 minutes after a release.

Level A: fully encapsulating vapor-protective suit with SCBA; highest respiratory, skin, and eye protection; required when skin contact or vapor exposure is possible.

Level B: chemical-resistant splash suit with SCBA; respiratory protection equivalent to Level A but only splash-level skin protection.

Level C: chemical-resistant suit with air-purifying respirator; only when atmosphere is known, IDLH is not exceeded, and oxygen is adequate.

Level D: structural firefighting gear or work uniform; no respiratory protection; only for atmospheres known to be non-hazardous.

SCBA rated service life is typically 30-60 minutes; working duration is shorter than rated duration due to exertion and stress.

Passive PPE (SCBA, encapsulating suit) adds heat stress; entry time must account for work rate, ambient temperature, and suit insulation.

Chemical permeation is measured by breakthrough time; degradation is loss of physical strength; permeation can occur with no visible damage.

Do not use air-purifying respirators for unknown concentrations, oxygen-deficient atmospheres (<19.5%), or IDLH conditions.

Decon corridor order from hot to cold: tool drop, gross decon, primary (technical) decon, secondary decon, then doffing area.

Gross decontamination removes the bulk of contaminant; technical decontamination uses soap and water scrubbing; secondary decon verifies reduction.

Decon methods: dilution, absorption, adsorption, chemical degradation, and isolation/disposal.

Emergency decon can be initiated with any available water source (ladder pipe, engine line, portable shower) before a formal corridor is set up.

Decon wastewater must be contained and disposed of as hazardous waste unless confirmed clean; runoff is a secondary contamination source.

Responders exiting the hot zone must be decontaminated before doffing PPE; doffing order proceeds from most contaminated to least contaminated.

Victims should be decontaminated before transport; hospitals may refuse contaminated patients, so notify receiving facilities.

Contaminated PPE and equipment require bagging and labeling with the material name and date for later disposal or cleaning.

Defensive operations include diking, damming, diverting, absorbing, and shutting off remote valves; offensive operations include product control inside the hot zone.

Dike far enough from the spill to contain the full volume: dike volume should be at least 1.5 times the spill volume.

Damming restricts flow; diversion channels move product to a controlled collection area; both require consideration of slope and downstream receptors.

Absorbents: universal (all liquids), oil-only (petroleum on water), and acid/caustic-specific; do not use water-reactive absorbents on reactive materials.

Overpack drums and salvage drums allow containment of damaged containers; overpack capacity must exceed the damaged container's volume.

Flammable liquid fires: use foam; AFFF is effective on hydrocarbon fuels but not on polar solvents (alcohols require AR-AFFF or alcohol-resistant foam).

Vapor suppression methods: foam blanket, vapor-suppressing agents, water spray, and covering the surface.

Do not apply water directly to water-reactive materials (e.g., sodium, calcium carbide) or to materials that react to produce toxic or flammable gas.

Response modes: rescue, defensive (containment), offensive (product control), and non-intervention (evacuation only).

Rescue is the highest-priority objective but must not be attempted without PPE and a viable plan; rescuer safety takes precedence.

The action plan must identify: current conditions, objectives, tactics, resources, and a safety plan for the operational period.

Defensive strategy is chosen when the material is unknown, PPE is inadequate, or the risk exceeds the benefit of offensive action.

Offensive strategy requires identification of the material, adequate PPE, a trained team, and a viable containment or control method.

Protective action decisions: evacuate when time permits and the hazard is growing; shelter-in-place when evacuation would move people through the hazard or time is short.

Spill control priorities: isolate, identify, notify, contain, and then control; do not commit to control before identification.

Termination criteria: objectives met or abandoned, decon complete, resources released, and the incident debriefed.

OSHA 29 CFR 1910.120 (HAZWOPER) covers emergency response: training levels, medical surveillance, PPE, and site safety plans.

HAZWOPER training: Awareness level, Operations level, Technician level, Specialist level, and Incident Commander level; refresher training is annual.

DOT 49 CFR 171-180 governs placarding, shipping papers, packaging, and emergency response information for transport.

CERCLA (Superfund) and the Clean Water Act establish release reporting and reporting requirements; the National Response Center receives reports.

RCRA (40 CFR 260-265) governs hazardous waste generation, storage, transport, and disposal.

SARA Title III (EPCRA) requires community right-to-know reporting and establishes Local Emergency Planning Committees (LEPCs).

The Emergency Planning and Community Right-to-Know Act requires facilities to report hazardous chemical inventories (Tier II) and release inventories (Tier I).

NFPA 471/472 cover response to hazardous materials incidents and recommended practices for responders; NFPA 704 is the identification system.

HAZWOPER Operations-level responders may perform defensive actions and must be trained annually; they cannot enter atmospheres that are IDLH.

Medical monitoring is required for responders who wear respirators or PPE; baseline and periodic exams are required.

The buddy system requires at least two responders in the hot zone and a backup team ready to rescue.

Heat stress is a primary PPE hazard; signs include confusion, hot dry skin, and collapse; cooling and hydration are the response.

Cold stress and hypothermia can occur with cryogenic exposure; frostbite and airway damage are immediate risks.

Site safety plan elements: hazard assessment, PPE levels, decon procedures, medical support, and emergency evacuation routes.

Exposure records must be maintained for the duration of employment plus 30 years under HAZWOPER.

Do not eat, drink, or smoke in the exclusion zone; wash hands and face after doffing and before eating.

The exclusion zone (hot zone) is where contamination is present; the contamination reduction zone (warm zone) is where decon occurs; the support zone (cold zone) is clean.

Zone boundaries are marked with barrier tape, cones, and entry control points staffed by a safety officer or entry control officer.

The safety officer has the authority to stop operations and must be independent of the operations section.

Emergency response plan must address pre-incident planning, notification, evacuation, and mutual aid.

Reportable quantities (RQs) are the threshold for CERCLA notification; releases below the RQ may still require state or local reporting.

Training records must document the level of training, dates, and instructor; refresher training is required annually for HAZWOPER responders.

Respirator fit testing is required annually and whenever a new respirator model is used; medical clearance precedes fit testing.

Hazardous waste manifests track waste from generator to disposal facility; the generator retains copies for three years.

Container shape clues: horizontal cylinders = flammable/compressed gas; vertical cylinders = gas; tank cars with domes = flammable liquid; MC-331 = anhydrous ammonia or propane.

Label colors: red = flammable, yellow = oxidizer, white = poison/toxic, blue = health hazard, green = nonflammable gas, orange = explosive.

The ERG's four-digit UN/NA number is indexed in the yellow-bordered pages; the blue-bordered pages list by material name.

Placards and labels are not reliable if the container is damaged, mislabeled, or the material is unknown; treat unknown materials as the worst case.

Odor is not a reliable indicator: some toxic gases (carbon monoxide) are odorless, and odor thresholds vary widely among individuals.

Water-reactive materials produce flammable or toxic gas on contact with water; examples include alkali metals, metal hydrides, and calcium carbide.

Oxidizers (e.g., nitrates, peroxides, chlorates) can intensify fire and cause spontaneous ignition when mixed with organic materials.

Corrosives have pH extremes; both acids and bases cause tissue damage, and the extent depends on concentration, contact time, and temperature.

Flammable range is bounded by LFL and UFL; concentrations within the range can ignite if an ignition source is present.

Flash point is the lowest temperature at which a liquid gives off enough vapor to form an ignitable mixture near its surface.

Boiling point and vapor pressure together determine how quickly a liquid produces vapor; low boiling point and high vapor pressure mean rapid off-gassing.

The vapor hazard of a spilled liquid is greatest at temperatures above its flash point and when the surface area is large.

Toxic exposure is expressed as concentration x time (ppm-minutes); short high exposures and long low exposures can produce different effects.

Reactive hazards include polymerization, decomposition, and incompatibility with water, air, or other materials; check the reactivity quadrant and SDS Section 10.

The SDS (formerly MSDS) has 16 sections; Section 6 covers accidental release measures, Section 8 exposure controls, Section 9 physical properties.

Risk assessment must consider the receptor: population density, sensitive environments, water intakes, and critical infrastructure downwind or downstream.

The first-arriving officer establishes command and remains until command is transferred formally to a higher-ranking or more qualified officer.

Unified Command is used when multiple agencies have jurisdiction; each agency retains authority for its own resources.

The Operations Section Chief directs tactical operations; the Planning Section Chief prepares the IAP and tracks resources.

The Incident Commander sets objectives; the Safety Officer monitors safety and can stop operations; the Liaison Officer coordinates with outside agencies.

Communications should include: nature of incident, location, material, quantity, injuries, resources needed, and staging area.

Staging areas are located in the cold zone, upwind and uphill, with a single entry and exit point.

The ERG's protective action distances are for the first 30 minutes; extend distances for larger releases, fire, or adverse weather.

Public warning methods include emergency alert systems, door-to-door notification, and media broadcasts; shelter-in-place instructions should specify closing windows and shutting off ventilation.

Chemical-protective clothing is selected by permeation data, not by appearance; check the manufacturer's compatibility chart for the specific material.

Fully encapsulating suits have a limited service life and require cooling; entry time is typically shorter than SCBA duration.

Glove selection must match the chemical; butyl, nitrile, neoprene, and Viton have different resistance profiles.

Structural firefighting turnout gear provides thermal protection but limited chemical resistance; it is not a substitute for chemical-protective clothing.

SCBA cylinders are hydrostatically tested every 5 years; visual inspection occurs before each use.

Do not remove PPE in the hot zone; doffing occurs in the contamination reduction zone after decontamination.

Respirator cartridge change schedules must be based on the material's breakthrough time, not on odor.

PPE ensembles must be compatible: suit, gloves, boots, and respirator must seal and not interfere with each other.

Decon solution: soap and water is effective for most materials; some materials require specific neutralizers (e.g., dilute acid for bases).

Do not use bleach on ammonia or on acids; mixing can produce toxic gas.

Decon of patients: remove contaminated clothing, wash skin with soap and water, and flush eyes with water for at least 15 minutes.

Gross decon is performed at the hot/warm zone boundary; technical decon is performed in the warm zone.

Decon station layout: one-way flow from dirty to clean, with separate lines for ambulatory and non-ambulatory victims.

Decon water temperature should be tepid; hot water increases absorption and cold water can cause hypothermia.

Contaminated runoff must be diked and collected; it is a hazardous waste unless tested and confirmed clean.

Decon effectiveness is verified by monitoring (e.g., radiation survey, pH paper, or colorimetric indicators) before doffing.

Diking and damming are defensive tactics; they require an anchor point and a containment volume larger than the spill.

Absorbents are applied from the outside edge of the spill inward to avoid spreading the material.

Foam blankets suppress vapor and extinguish flammable liquid fires; foam must be applied gently to avoid breaking the blanket.

Foam expansion ratio: low expansion (up to 20:1), medium (20-200:1), high (200-1000:1); high-expansion foam is used for confined spaces.

Do not use water on a flammable liquid fire unless it is a fine spray for cooling; a solid stream can spread the fire.

Plugging and patching can stop a leak from a container; the patch material must be compatible with the product.

Transfer operations require grounding and bonding to prevent static ignition.

Containment of a gas release is generally not possible; control focuses on isolation, dispersion, and ignition source elimination.

The response objective hierarchy: life safety, incident stabilization, property conservation, and environmental protection.

The size-up should include: container type, material, quantity, fire or not, wind direction, terrain, exposures, and available resources.

Defensive operations are appropriate when the material is unidentified, the atmosphere is IDLH, or the risk of offensive action outweighs the benefit.

Offensive operations require a trained team, adequate PPE, a viable control method, and a backup team.

The IAP should be written for incidents lasting more than one operational period or involving multiple agencies.

Evacuation distances should be based on the ERG, plume modeling, or the incident commander's judgment; they should be reassessed as conditions change.

Termination includes debriefing, documentation, critique, and release of resources.

After-action review should identify what worked, what did not, and what changes are needed for future responses.

OSHA 1910.120 requires a site-specific safety and health plan for hazardous waste operations.

The HAZWOPER standard requires medical surveillance for employees exposed above permissible exposure limits for 30 or more days per year.

DOT requires emergency response information to accompany shipping papers; this is often the ERG or a equivalent document.

The Clean Air Act and Clean Water Act impose reporting and cleanup obligations for releases.

The Toxic Substances Control Act (TSCA) regulates chemical substances and requires reporting for new chemicals.

The Resource Conservation and Recovery Act (RCRA) requires hazardous waste to be tracked with a manifest and stored with proper labeling and containers.

The Emergency Planning and Community Right-to-Know Act requires facilities to report releases and inventories to the LEPC and state.

NFPA 472 defines competencies for hazardous materials responders, including awareness, operations, technician, and specialist levels.

Hot zone entry requires a buddy and a backup team; the backup team must be dressed and ready to rescue.

Entry control logs record name, time in, time out, and air supply status for each entrant.

The safety officer must be trained and empowered to stop unsafe operations.

Heat stress management includes work-rest cycles, hydration, cooling, and monitoring for signs of heat exhaustion or heat stroke.

Cold stress management includes layered clothing, warming areas, and monitoring for frostbite and hypothermia.

Exposure to hazardous materials can cause acute and chronic effects; medical surveillance monitors for both.

Responders must not eat, drink, or smoke in the exclusion or contamination reduction zones.

Post-incident medical evaluation is required for responders who may have been exposed to hazardous materials.

The DOT placard for a material with multiple hazards shows the primary hazard class; subsidiary hazards appear on shipping papers.

The NFPA 704 white quadrant special hazards: OX = oxidizer, W with a slash = reacts with water, SA = simple asphyxiant.

Container markings: UN/NA numbers, proper shipping names, and orientation arrows; missing markings suggest an unknown or mislabeled material.

Pipelines carry a commodity marker but the product may change; verify with the operator before assuming contents.

The senses are a last-resort clue: never intentionally smell or touch an unknown material.

Human behavior (evacuation, panic, or collapse) can indicate the presence and location of a release.

Occupancy clues: laboratories, dry cleaners, agricultural suppliers, and paint stores suggest specific material types.

The ERG's initial isolation distances are based on the material and container size; they are minimums, not maximums.

The dose-response relationship describes the relationship between exposure and effect; higher doses generally produce more severe effects.

Acute effects appear soon after exposure; chronic effects appear after repeated or long-term exposure.

Sensitization can occur with repeated exposure; subsequent exposures may produce a more severe reaction.

The permissible exposure limit (PEL) is the OSHA regulatory limit; the TLV is a recommended limit from ACGIH.

The immediately dangerous to life or health (IDLH) value is used to select respiratory protection; air-purifying respirators are not used in IDLH atmospheres.

The explosion hazard of a flammable liquid depends on the vapor pressure and the flash point; a liquid with a flash point below 100°F is a flammable liquid.

The reactivity hazard includes the potential for polymerization, decomposition, and reaction with water or air.

The environmental hazard includes toxicity to aquatic life, persistence, and bioaccumulation.

The first-arriving unit should establish command, size up the incident, and request additional resources.

The incident commander should establish a command post in the cold zone, upwind and uphill.

The command post should have communications, a log, and access to the ERG and SDS.

The liaison officer coordinates with outside agencies, including hospitals, utilities, and environmental agencies.

The public information officer releases information to the media; only the PIO or IC should speak to the media.

The planning section develops the incident action plan and tracks resources and situation status.

The logistics section provides resources, including PPE, food, water, and medical support.

The finance/administration section tracks costs and handles reimbursement.

Level A suits are tested for chemical permeation and must be selected for the specific material.

Level B suits provide splash protection but not vapor protection; they are used when the atmosphere is not IDLH and skin contact is limited.

Level C requires an air-purifying respirator with the correct cartridge and a known atmosphere.

Level D is not appropriate for any hazardous materials incident.

Respirator fit testing must be performed annually and whenever a new respirator model is used.

SCBA cylinders must be inspected before each use and hydrostatically tested every 5 years.

PPE must be decontaminated before doffing; contaminated PPE is bagged and labeled.

Heat stress is a major risk with Level A suits; cooling and work-rest cycles are required.

Emergency decon is the immediate removal of contamination using any available water source.

Gross decon removes the bulk of the contaminant; technical decon uses soap and water and scrubbing.

Secondary decon verifies that contamination has been reduced to an acceptable level.

Decon of equipment: tools and PPE are decontaminated or bagged for disposal.

Decon of patients: remove clothing, wash with soap and water, and flush eyes for at least 15 minutes.

Decon runoff must be contained and disposed of properly.

Decon station layout should provide one-way flow from dirty to clean.

Decon effectiveness should be verified by monitoring before doffing.

Diking and damming are defensive tactics that contain the spread of a spill.

Absorbents are applied from the outside edge inward.

Foam blankets suppress vapor and extinguish flammable liquid fires.

Foam expansion ratio: low, medium, and high expansion.

Do not use water on a flammable liquid fire unless it is a fine spray for cooling.

Plugging and patching can stop a leak from a container.

Transfer operations require grounding and bonding.

Containment of a gas release focuses on isolation and dispersion.

The response objective hierarchy: life safety, incident stabilization, property conservation, and environmental protection.

Size-up includes container type, material, quantity, fire, wind, terrain, exposures, and resources.

Defensive operations are appropriate when the material is unidentified or the atmosphere is IDLH.

Offensive operations require a trained team, adequate PPE, a viable control method, and a backup team.

The IAP is written for incidents lasting more than one operational period.

Evacuation distances should be based on the ERG or plume modeling and reassessed as conditions change.

Termination includes debriefing, documentation, critique, and release of resources.

After-action review identifies what worked and what needs improvement.

OSHA 1910.120 requires a site-specific safety and health plan for hazardous waste operations.

HAZWOPER requires medical surveillance for employees exposed above PELs for 30 or more days per year.

DOT requires emergency response information to accompany shipping papers.

The Clean Air Act and Clean Water Act impose reporting and cleanup obligations.

TSCA regulates chemical substances and requires reporting for new chemicals.

RCRA requires hazardous waste to be tracked with a manifest.

EPCRA requires facilities to report releases and inventories to the LEPC and state.

NFPA 472 defines competencies for hazardous materials responders.

Hot zone entry requires a buddy and a backup team.

Entry control logs record name, time in, time out, and air supply status.

The safety officer must be trained and empowered to stop unsafe operations.

Heat stress management includes work-rest cycles, hydration, and cooling.

Cold stress management includes layered clothing and warming areas.

Medical surveillance monitors for acute and chronic effects.

Responders must not eat, drink, or smoke in the exclusion or contamination reduction zones.

Post-incident medical evaluation is required for responders who may have been exposed.