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Ok now that we have a idea of what hazardous materials are, now we need to figure out where we will find them. So lets start with the basics. There are several methods of transporting Hazardous Materials.
Roadways
Railroads
Waterways
Airways
Pipelines

These are in all areas, and when in the course of your duties you might encounter one or more of them. You could possible run into a combination of these at 1 time. Several years ago a jet crashed in Detroit onto the highway, There you could have it by air and road, or how about a accident that hits a pipeline. Granted you are not going to be cleaning up the mess, but you might have to recover the vehicles.
Other places that you will encounter hazardous materials are:
Service Stations
Hardware stores
Doctors offices
Schools
Farm supply stores
Farms
Residences
Welding shops
Freight forwarding companies
Stores

All of these will have some hazardous materials in one form or another as these are common locations. And the big factor is that most of the above have products that are transported by cars, or light trucks. We go to the store and shop, never considering what would happen if the Clorox and Vinegar and Bleach were to get mixed up or broken open in a accident. I am sure that anyone in the general area that is trying to rescue you might not be able to do so. And if you are in a semi rural area,, help is sometimes awhile getting to you. Now I know that most of this is worst case, but it can and does happen.
And for all you home welders, and people that transport propane tanks, remember that they are pressurized. If the valve were to get knocked off, you have a unguided missile that is loose in the back of the truck, or in your trunk. When I learned how to scuba dive, we were told of a dive shop in California, ( and shown pictures ) that had a loaded tank take off, after the valve broke off. It went through 3 cinderblock walls and took out a large tree before stopping in a engine block of a parked car.
And what about gardeners, and farmers, they transport all kinds of hazardous materials in the form of fertilizers and pesticides. And alot of pesticides are EXTREMELY TOXIC AND HAZARDOUS. Some of them are fast acting, and only a couple of drops of them will do you in.
Or how about the local Fed Ex, or UPS truck, lord knows what they might be delivering. You would be amazed that the quanity of hazardous materials that UPS carries daily. They are the largest carrier of hazardous materials. And some of it is in real small packages. Medical supplies, samples, tests, radioactive materials, chemicals, explosives, if you can name it and they ship it.
Oh yeah, I forgot, the growing proplem of drug labs, has caused the transportion of chemicals for making them, in cars and campers. You should know that most, if not all Law Enforcement agencies, once they find a drug lab, exit the location right away because of the risks from the chemicals. People that clean up these locations require special protective suits so that they do not get exposed to the EXTREAMLY TOXIC SUBSTANCES involved.

So you see the general overview of the problem, you never know where you might encounter hazardous materials, and as a first responder, you must be knowledgable of, and prepared to take the actions necessary to protect people, the environment, and property. So now the new term " INCIDENT ASSESSMENT " come into play. If you happen to find a accident that involves motor vehilces you should look at the scene before you get out to provide help. After all you most likely will be calling in to your dispatcher the information and location of the accident. While you are doing that , is there smoke ?, or steam from the radiator. Is there a steady flow of liquids from the vehicles ( could be a gas leak ), is there a cloud of gas hovering over the vehicles. All of these might be a sign of a hazardous material. If you were to encounter a rolled over welding truck with cylinders all over the area, I would look for a upwind area to park and to respond from. You can not see alot of hazardous materials, as they are sometimes colorless, and odorless. Or they are a liquid that eats skin and of course your boots and clothes. I can't think of a worse sight than a sick, naked tow truck driver, that needs rescue , when they were trying to rescue a injured person.
Incident Assessment, means that you should assess the following things BEFORE YOU ATTEMPT a rescue:

Risk to rescuers
Probability of victim survival
Difficulty of rescue
CAPABILITIES and RESOURCES of people on-scene
Constraints of time and distance
Possibility of explosions
Available escape routes and safe havens

You should be able to do this assessment in the minute or so that it takes you to notify someone of the accident. A simple car in a ditch is one thing, but a car under a gasoline tanker is another thing. 9000 gallons of gas makes one big bang.
Alot of the risks are based on what YOU have for equipment with you when you find the accident. Most tow trucks have a pry bar, fire extingisher, and shovel. With a fire extingisher you can attempt to put out a fire, you can also shovel dirt onto it !!!!. Or use the shovel to control or divert a liquid spill from the area that you have to work in. Or a pry bar to help open the doors, or other things that you need to move.
Granted the rush that you get from encountering a accident, and knowing that you might need to help is great, but you do not want to be involved in making the incident worse. I personally hope that we do not have anyone in the industry what wants to be a dead hero, we already lose too many people to drivers that run us over while we are working.
So I guess that the point that everyone needs to remember is, take your time, and think about what you are getting involved in. After all, the stuff you might be playing in, can possibly kill you