☣️ UN 3209 • CLASS 4

UN 3209 — Metallic substance, waterreactive, self-heating, n.o.s.

Placard: Dangerous When Wet. ERG Guide 138. Training/quick-reference only — use current ERG + SOP/SOG for incident-specific actions.

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⚠️ Verification required: Broad or variable material category; verify exact product, SDS and shipping papers.
⚠️ This page is a quick-reference aid. For real incidents: stage upwind, isolate, deny entry, request Hazmat early, and consult the current ERG + SOP/SOG.

UN 3209 covers metallic water-reactive material. It may be powder, granules or pieces, and exact composition determines the safest control method.

Hazard overview: The key danger is water contact. Moisture can create heat, flammable gas and ignition, especially with powders or self-heating materials.

Response guidance: Isolate the release, keep it dry and prevent runoff. Use dry sand, soda ash, dry limestone or approved dry chemical media; keep water and foam away from the product.

Firefighter training notes: Train crews to recognize dangerous-when-wet placards, keep product dry, deny entry to low areas, and avoid using hose streams on unknown reactive solids or liquids.

Regulatory context: Class 4 dangerous-when-wet entries require strict moisture control, compatible packaging and product-specific SDS verification during transport and storage.

Storage & handling: Store dry, tightly sealed and away from water, humidity, sprinklers, acids and incompatible extinguishing agents. Keep spill control media dry and dedicated.

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UN 3209 Quick Details

UN 3209
Product name: Metallic substance, waterreactive, self-heating, n.o.s.
DOT Class: 4
Placard type: Dangerous When Wet
ERG Guide: 138 (check current ERG)
Initial isolation: ERG 138: isolate spill 25m all directions; if fire or large spill, isolate 800m and evacuate 800m downwind

Common Hazards of UN 3209

  • Water-reactive metallic material can generate flammable hydrogen or other gases.
  • Moisture or humid air may cause ignition, heat generation or violent reaction.
  • Fine powders may burn rapidly and re-ignite after knockdown.
  • Containers may rupture when heated or contaminated with water.
  • Fire can produce metal oxides and irritating or toxic smoke depending on composition.
  • Wet runoff can spread reaction and fire hazards.
  • Exact metal or alloy must be verified before selecting extinguishing media.

Chemical Identity & Physical Properties

Metallic solid or powder, appearance varies by specific metal. May be gray, silver, or dark colored. Odorless in dry state.

Also known asWater-reactive metalSelf-heating metallic materialPyrophoric metal substance
AppearanceMetallic solid or powder, appearance varies by specific metal. May be gray, silver, or dark colored. Odorless in dry state.
Flash PointNot applicable (reacts with water to produce flammable gas)
Boiling PointNot applicable (solid metal, varies by specific substance)
Vapor DensityNot applicable (solid material)
Water ReactivityReacts with water producing flammable hydrogen or other gases; may ignite spontaneously on contact with moisture or humid air
Chemical details are general reference only. Always verify with current SDS, ERG, and SOP/SOG.

Fireground Response Guidance — UN 3209

Extinguishing Media

Dry sand, dry chemical, soda ash; DO NOT use water, foam, CO2, or halogenated agents

PPE Requirements

⚠️ Level B minimum with SCBA; face shield, chemical-resistant gloves; avoid moisture exposure during handling

Use SCBA, face/eye protection and chemical-resistant protective clothing. Avoid carrying wet tools or applying wet absorbents near the release.

Isolation & Evacuation

ERG 138: isolate spill 25m all directions; if fire or large spill, isolate 800m and evacuate 800m downwind
Always confirm protective actions with the current edition of the Emergency Response Guidebook (ERG Guide 138).

First Actions for a UN 3209 Incident

  • Call 911 and the emergency response number on the shipping paper, if available.
  • Keep unauthorized personnel away and establish incident command before close approach.
  • Stay upwind, uphill and upstream; avoid low areas where vapors or gases may collect.
  • Avoid breathing vapors, dust, smoke or decomposition products and avoid skin or eye contact.
  • Do not touch damaged containers or spilled material without appropriate PPE and monitoring.
  • Ventilate confined spaces only if trained, equipped and authorized by incident command.
  • Use ERG, SDS, shipping papers and atmospheric/radiation monitoring for final isolation and control decisions.
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📋 Copy & Share Field Card

UN 3209 — Metallic substance, waterreactive, self-
HAZMAT RADIO NOTE — UN 3209 Product: Metallic substance, waterreactive, self-heating, n.o.s. Class 4 / Dangerous When Wet / ERG 138 PPE: Level B minimum with SCBA; face shield, chemical-resistant gloves; avoid moisture exposure during handling ISOLATION: ERG 138: isolate spill 25m all directions; if fire or large spill, isolate 800m and evacuate 800m downwind ACTION: Stage upwind · Isolate · Deny entry · Request HazmatRADIO

Use for: Quick radio or face-to-face size-up. Short, structured, field-ready.

SMS WhatsApp
=== IC HAZMAT BRIEFING === UN 3209 — Metallic substance, waterreactive, self-heating, n.o.s. Class: 4 | Placard: Dangerous When Wet | ERG Guide: 138 Appearance: Metallic solid or powder, appearance varies by specific metal. May be gray, silver, or dark colored. Odorless in dry state. Water Reactivity: Reacts with water producing flammable hydrogen or other gases; may ignite spontaneously on contact with moisture or humid air Extinguishing: Dry sand, dry chemical, soda ash; DO NOT use water, foam, CO2, or halogenated agents PPE: Level B minimum with SCBA; face shield, chemical-resistant gloves; avoid moisture exposure during handling Isolation: ERG 138: isolate spill 25m all directions; if fire or large spill, isolate 800m and evacuate 800m downwind — Key Hazards — • Water-reactive metallic material can generate flammable hydrogen or other gases. • Moisture or humid air may cause ignition, heat generation or violent reaction. • Fine powders may burn rapidly and re-ignite after knockdown. — First Actions — • Call 911 and the emergency response number on the shipping paper, if available. • Keep unauthorized personnel away and establish incident command before close approach. • Stay upwind, uphill and upstream; avoid low areas where vapors or gases may collect. • Avoid breathing vapors, dust, smoke or decomposition products and avoid skin or eye contact. SOURCE: allfirefighter.com/hazmat/un/metallic-substance-waterreactive-self-un-3209 | Always use current ERG + SOP/SOGIC BRIEFING

Use for: Incident command briefing, staging area whiteboard, or pre-entry team brief.

SMS (short)
UN3209 Metallic substance, waterreactive, self-heating, n.o.s. Cls4 ERG138 | allfirefighter.com/hazmat/un/metallic-substance-waterreactive-self-un-3209SMS / 160 CHAR

Use for: Quick text to command or incoming units. Fits in a single SMS.

⚠️ Quick-reference only. Always use current ERG + SOP/SOG for incident-specific actions. Page: https://allfirefighter.com/hazmat/un/metallic-substance-waterreactive-self-un-3209

Related UN Numbers in Class 4

Discovery block for training / quick reference. Always consult the current ERG + your SOP/SOG for operations.
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Frequently Asked Questions about UN 3209

UN 3209 is Metallic substance, waterreactive, self-heating, n.o.s.. It should be treated according to ERG 138 and the exact shipping papers or SDS.

It reacts with water or moist air, releasing flammable gas and potentially igniting.

Do not apply water directly unless product-specific guidance confirms it is safe. For dangerous-when-wet materials, water can release flammable or toxic gases.

Heat may increase pressure, worsen decomposition, release toxic or irritating gases, or intensify fire depending on the material.

Use positive-pressure SCBA and chemical-resistant protective clothing suitable for the product. Upgrade protection when the identity, concentration or release size is uncertain.
Sources (high level): DOT/PHMSA marking & class concepts + ERG usage principles. This page does not reproduce ERG guide text—always consult the current ERG for incident-specific protective actions.