Chemical Profiling

A Safe Approach for First Responders

In discussing with first responders what they should do at a hazardous materials call, I was given comments such as, “I fight fires; I don’t do chemicals” and “We’ll just let the hazmat team handle it; the fire companies will stand by.”

This type of comment is not uncommon. Many fire departments don’t have dedicated hazmat teams because of funding, lack of interest, or insufficient run volume to justify one. Some may think hazmat response is more dangerous than general firefighting. But is it? Why do any of us do “special” jobs, be it rescue, hazmat, or US&R? What makes it possible for us to do them? Training, knowing the hazards, and knowing our equipment prepare us to do the job, whatever it may be. Hazmat response is no different.

Regardless of department size or type, we all do hazmat! EMS runs present us with biologic hazards. Structure fires present us with chemicals such as arsine, acrolein, phosgene, and hydrogen cyanide, to name a few. If you have highways, railroads, navigable waterways,1 airports, industrial parts of town, dry cleaners, or a hardware store-be it a chain or a mom-and-pop-you do hazmat. And an engine or truck company will arrive before the hazmat team. So it is up to that officer and those company members to know what to do to ensure their safety first and then the safety of the public. To do otherwise is a disservice to yourself, your family, your coworkers, and the public.

Hazmats are defined as substances capable of posing an unreasonable risk to health, safety, and property. They can be grouped into four basic categories:

1. Commercial fixed sites, such as manufacturing, agricultural, or mercantile centers.
2. Nonstructural locations such as gas in pipelines, landfills, or electrical transformers.
3. Transportation corridors such as highways, railroads, or navigable waterways.
4. Residences, which, of course, are self-explanatory.

If you are the first-due officer at one of the sites above and no hazmat team is available, or if the hazmat team is delayed, what would you do?

Ludwig Benner, one of the principal forces in hazmat, gave us the DECIDE concept to follow when evaluating actions during hazmat responses.

D Detect the presence of hazardous materials.

E Estimate likely harm without intervention.

C Choose response objectives.

I Identify your action options.

D Do the best option.

E Evaluate progress.

The International Association of Fire Fighters uses a decision-making tool similar to DECIDE, but it is broken down into four action steps. The mnemonic is APIE:

A Analyze

P Plan

I Implement

E Evaluate

Whichever tool you use, it is imperative that you know how to obtain a chemical profile. Chemical profiling allows us to determine the hazards to first responders and the public, the acute and chronic effects of those hazards, the signs and symptoms of exposure to/contamination of the hazard, the routes of entry into the body, and the agents’ toxicity and lethality.

In addition to Material Safety Data Sheets (MSDS) for information on specific chemicals, fire departments generally use two references to research chemicals: the Emergency Response Guidebook (ERG), developed jointly by Transportation Canada (TC) and the U.S. Department of Transportation (U.S. DOT), and the National Institute for Occupational and Safety and Health (NIOSH) Pocket Guide to Chemical Hazards.

THE ERG

The ERG, designed specifically for first responders, should be the primary resource in the initial phase of a dangerous goods/hazmat incident. It provides vital information on the 3,400-plus chemicals listed therein. The book is broken down as follows:

• Pages 1 to 4: Instructions for using the book; the information contained in the color-coded sections.
• Yellow-bordered pages. Agents in numerical order by a four-digit ID number. Example: ID No. 1005; Guide No. 125; Name of Material, Ammonia, Anhydrous.
• Blue-bordered pages: Agents in alphabetical order by material name. Example: Name of Material, Ammonia, Anhydrous; Guide No, 125; ID number, 125.
• Orange-bordered pages: 62 recommendations or guides, divided into two-page sections, that present emergency response information for protecting the first responder and the public. Each guide covers a group of materials that possess similar chemical and toxicological characteristics:

  -First (left page) “Potential Hazards – Flammability/Toxicity”: The first hazard listed is the most dangerous or primary hazard.

  • Public Safety – Protective clothing and actions.

  -Second (right page) “Spill and Fire Response Procedures, First-Aid Procedures.”

• Green-bordered pages: A list by ID number of “Toxic Inhalation Hazard (TIH)” materials, including weapons of mass destruction (WMD) and water-reactive materials that give off toxic gases when contacted by water.
• Pages 7-13: International Notification phone numbers as well as pertinent information to provide to the source being notified.
• Page 14: Hazard Classification System listing of the nine hazard classes and the divisions within each class.
• Pages 15-17: “Table of Placards,” to be used ONLY if the responder is unable to identify materials being transported by their chemical name or ID numbers.
• Pages 18-19: “Rail Car and Road Trailer Silhouettes and Markings” with corresponding guide numbers, to be used ONLY if the responder is unable to identify the product by chemical name or ID number.
• Pages 20-23: Materials/dangerous goods shipped by intermodal containers with ID markings and codes.
• Page 24: If an entry is highlighted in the yellow- or blue-bordered pages and there is no fire, go directly to the “Table of Initial Isolation and Protective Action Distances” (green-bordered pages) and look up the ID number and name of material, to obtain the protective action distances. If there is a fire, or if fire is involved, go directly to the appropriate guide (orange-bordered pages) and use the evacuation information shown under “Public Safety.”
  Note: A guide number supplemented with the letter “P” indicates that the material may undergo violent polymerization if subjected to heat or contamination.
• Pages 350-351: “Protective Clothing Structural Firefighting Protective Clothing (SFPC) and Chemical Protective Clothing (CPC).”
• Pages 352-353: “Fire, Spill, and Vapor Control.”
• Pages 354-357: “Criminal/Terrorist use of WMD Agent.”
• Pages 358-365” “Glossary of Terms.”

It cannot be stressed enough that the ERG is our primary reference for the initial phase of an incident. It is designed for first responders. The more familiar we become with the ERG, the more confident we will be in using it and the safer we will be during an incident.

As with all things, however, competent use of any tool includes knowing its limitations. Whether it is our breathing apparatus, our fire gear, or even ourselves, everything has limits, and we must be aware of those limits. Knowing those limits will prevent us from going too far in a given situation and from becoming part of the problem instead of the solution.

ERG Limitations

The ERG also has limitations.

1. It is good only for up to the first 30 minutes of an incident; then, you must consult other resources to mitigate the incident successfully.
2. It lists about 3,400-plus chemicals. To put that into perspective, more than 3,000 new compounds are developed annually. They are added to the 100,000 existing compounds and 5 million mixtures and formulations already being used in industry. Of those 3,000 new compounds developed yearly, research labs test only about 400 of them each year; some of those tests take up to eight years for satisfactory results. Even after that time, all the harmful effects may not be known. The ERG provides information on only a fraction of the chemicals in use today.
3. It does not provide chemical-specific information-i.e., chemical/physical properties, target organs affected, respiratory protection needed, and so on. You may ask why we should use the ERG since it has these limitations. Why do we use any piece of equipment that has limitations or shortcomings? The answer is obvious: It is better than not having anything at all to use in a hazmat incident or following the “old school” way of approaching a leaking vessel and using the senses of smell and taste to try to determine if the chemical is hazardous.

NIOSH POCKET GUIDE TO CHEMICAL HAZARDS

The first-due officer may also consult The NIOSH Pocket Guide to Chemical Hazards for assistance in chemical profiling. However, as stated previously, the ERG is the reference to consult in the initial phase of a hazmat/dangerous goods incident.

Many fire departments carry The NIOSH Pocket Guide along with the >ERG for hazardous-materials incidents. It is an outstanding book for detailed chemical information-a “playbook” for chemicals. It tells you what a chemical will do in air or water, its physical state (solid/liquid/gas), and its harmful effects on responders.

It was designed as a source of industrial hygiene information for workers, employers, and occupational health professionals. In other words, it was designed primarily for industry, not first responders. This is evident from the setup. However, once the basics are known, it becomes relatively easy to use. The book provides information on 677 of the industrial chemicals most commonly found in the work environment.

The Guide is set up as follows:

• Page viii: instructions for using the Guide -the abbreviations and codes used in the book, the fields of information, and their meanings.
• “Chemical Name” is listed in the blue box in the top-left portion of each chemical table. In other portions of the book, it is also referred to as the “Primary Name.”
• “Structural Formula” section: for those who have attended the National Fire Academy chemistry course. Chemical structural formulas are to the right of the chemical name.
• “CAS Number”: a unique number assigned to chemicals by the Chemical Abstract Services in Columbus, Ohio. This number has no chemical significance. The CAS registry is the largest and most current database of chemical substance information in the world, with more than 30 million organic and inorganic substances and approximately 4,000 substances added daily.
• The “Registry of Toxic Effects of Chemicals (RTECS)” number is based on scientific literature. The data are provided to obtain additional toxicological information and are arranged in alphabetical order by prime
• Immediately Dangerous to Life and Health (IDLH): the concentrations at which the chemical is IDLH and the airborne concentrations from which a worker could escape without injury or irreversible health effects in case of failure of the respiratory protection.
• “Conversion Factors for converting parts per million (ppm) to milligrams per cubic meter mg/m3”: This information is not necessarily applicable to first responders.
• “DOT ID and Guide Number Lists” indicate that the chemical is regulated by the Department of Transportation. Note : Many DOT numbers are not unique for a specific substance.
• “Synonyms and Trade Names”: an alphabetical list of common synonyms and trade names for each chemical listed. Numerous chemicals are referred to by more than one name, making this section extremely important for use in chemical profiling.
• Exposure Limits: Time weighted averages (TWA) are NIOSH Recommended Exposure Limits (REL) based on a 10-hour day in a 40-hour workweek. A short-term exposure limit (STEL) is a 15-minute exposure that should not be exceeded anytime during a workday. A worker may be exposed for this period four times within a workday with a one-hour break in between incursions. A ceiling REL should not be exceeded any time during a workday. Any substance NIOSH considers to be an occupational carcinogen is designated by the notation “Ca.” NIOSH exposure limits are recommendations only. OSHA is a law-making agency with the power to impose monetary fines on agencies that violate work practices, hence its regulations must be observed . OSHA TWA Permissible Exposure Limits (PEL) are based on eight-hour workdays, 40 hours per week, with short-term exposure limit and ceiling values expressed as well.

The data provided in the exposure limits section have a direct link to the substance’s toxicity and are important for ensuring first responder safety as well as for chemical profiling. Do not ignore them or treat them lightly.

• “Measurement Method”: used to determine exposure methods for chemicals or substances-not necessarily applicable for first responders.
• “Physical Description”: includes the appearance and odor of a substance, whether it can be shipped as a liquefied compressed gas, and if it has a major use as a pesticide.
• “Chemical and Physical Properties”: includes abbreviations for each substance of the “playbook,” those indicators that specifically tell what a chemical will do under different circumstances
  A chemical listed with flammability/combustibility classes is not to be confused with one of the nine hazard classes used by the DOT. OSHA classifies flammable/combustible liquids based on temperature:

  -Class I A flammable liquid-flash points < 73°F and boiling points below 100°F.

  -Class I B flammable liquid-flash points < 73°F and boiling points = or > 100°F.

  -Class I C flammable liquid-flash points = or > 73°F and below 100°F.

  -Class II combustible liquid-flash points = or > 100°F and below 140°F.

  -Class III A-flash points = or > 140° F and below 200°F.

  -Class III B combustible liquid-flash points = or > 200°F.

  -“Personal Protection and Sanitation”: summarizes practices for each substance supplementing general work practices such as no eating, drinking, or smoking in areas where chemicals are present; not necessarily for use by first responders.

• “Respirator Selection”: As first responders, we have the highest level of respiratory protection available.
• “Incompatibilities and Reactivities”: They are listed for each substance. When profiling chemicals, it is important to note first whether the substance is reactive or incompatible with water because water is our primary decon solution.
• “Exposure Routes, Symptoms, and Target Organs”: lists toxicologically important entry routes, potential symptoms of exposure, and affected target organs.
• First Aid: emergency procedures for eye and skin, inhalation, ingestion, and contact with toxic substances.
• Appendices: Listed are potential occupational carcinogens, the OSHA regulated carcinogens, supplementary exposure limits, substances with no established RELs, OSHA respirator requirements for selected chemicals, and vacated PELs.2

In column two is a page from the current Guide that presents information on the common industrial chemical ammonia, a substance that all of us have dealt with at one time or another. It is used for fertilizer in agriculture as well as a refrigerant in industry. DOT classifies it as a hazard class 2 nonflammable gas.

Even though the Guide is not viewed as a primary resource, it has a great deal of information that firefighters and emergency responders who understand its application and limitations can use.

APPLICATIONS AND LIMITATIONS

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1. Numerous abbreviations are used. In an emergency, deciphering these abbreviations and the codes used may be time consuming if you are not familiar with them.
2. Information is provided only for 677 commonly used industrial chemicals out of 3,000-plus substances developed annually.
3. The analytical methods used in the Guide are based on controlled standards-i.e., ambient temperature is 68°F with an atmospheric pressure of 14.7 psi at sea level. First responders do not work in controlled environments. A substance that boils at 120°F spilled on a highway in 100-percent humidity on asphalt in the middle of the day in Denver, Colorado, may act differently than it would in a 68°F setting in a lab in Ohio. So while the Guide is of great use for chemical profiling, you must keep in mind the limitations to ensure your safety.

When I started firefighter training for one of the suburban Cincinnati departments, I was not particularly interested in hazmat. All I wanted to do was fight fire. The classes on fire behavior were of no interest to me either. Who cared about the fire triangle or fire tetrahedron, or whatever it was called? But when I learned the direct correlation between firefighting and the knowledge of chemical and physical properties and the types of poisonous gases given off at fires, the emergency to which I wanted to respond more than any other, I discovered that every run is a hazardous-materials run. Then, I got it: The only way I could be a good firefighter was to learn every aspect I could about the enemy and the only way I could ensure my safety-and by extension take care of my personal family and work family-was to learn as much as I could about defeating the enemy. The funny thing is that the only thing I have learned 15 years later is how much I don’t know, but I am learning.

In addition to the two publications discussed above, there are other resources that can help with chemical profiling, including shipping papers, material safety data sheets, placards, and markings. It is vital that we learn how to perform a quick, efficient, and accurate chemical profile if we are to operate safely.

Endnotes

1. Those waters that are subject to the ebb and flow of the tide and/or are presently used, or have been used in the past, or may be susceptible for use to transport interstate or foreign commerce.

2. In 1989, OSHA determined it was not practical to set PEls for thousands of individual chemicals and enacted generic rulemaking that broke chemicals into categories. This method was challenged in a 1989 court case. The District Court of Appeals struck down (vacated) the 1989 PEL revisions. OSHA, therefore, was forced to revert to the older limits, which afford less protection. For OSHA to set new PELs, it would have to collect specific evidence for each substance so the risk-benefit analysis could be reviewed.

Robert Shelton, a 15-year veteran of the fire service, is a member of the Cincinnati (OH) Fire Department, where he is a hazmat specialist/rescue tech on Squad 14. He is also a member of the Hamilton County (OH) US&R task force. He is a fire science and hazmat instructor for Cincinnati State Technical and Community College, a classroom presenter for FDIC, and a contributor to the Fire Engineering