Saturday, July 23, 2011

The Chemistry of Flame Retardants: Part Two-The Environmental Impact of Brominated Flame Retardants

Brominated flame retardants show some of the complexities of the problems faced with many of the materials that we use in life. Obviously, the effects of fires are terrible. There is severe, acute danger to the ease of ignition and flammability associated with the many materials that our daily life is so dependent on. The incorporation of flame retardants immediately reduces this problem. But the use of flame retardants isn't without its own pitfalls. The second most common flame retardant in commercial use is polybrominated diphenylethers (PBDE). These compounds can have up to ten bromine atoms attached to them, and their use is dependent on the number of bromines that are attached to the diphenylether. In chemistry, a difference of one atom can make massive changes to its chemical behaviour. For example, cyanide is one carbon atom triple bonded to one nitrogen atom, and is extremely poisonous. But the atomospere is 75% N2, which is one nitrogen atom triple bonded to one nitrogen atom, and is completely innocuous. These two compounds differ only be one atom. The three most common PBDEs are deca, penta, and octa (10, 5, and 8 bromine atoms). One of the problems with PBDEs is that they are not chemically bonded to any of the materials that they are incorporated into, they are simply physically mixed in. This means that they can be leached from the material and into the environment. 

To examine the problem of their presence in the environment, we need to look at what characteristics makes the chemicals good flame retardants. The chemicals need to be stable and they need to last long. If they weren't, the chemicals wouldn't stay around long enough in the materials that they are incorporated into and eventually those materials would become easily flammable again. So PBDEs are very stable and will last a long time without degrading. This means that if they leach into the environment they will not break down, but persist for years. The other downside of their ability to leach out of materials is a decrease in flame retardance over time. 

PBDE have been detected in arctic life. This suggests that they can be transported through the environment a long way from where they were initially released into it. This is termed "long-range transport". There is also evidence of "bioaccumulation". The chemical is taken up by organisms low on the food chain, and those organisms are in turn take up by organisms higher up on the food chain. The result is that what was a small amount of chemical in an organism low on the food chain becomes a much larger amount of chemical in organisms higher up on the food chain. This process happens when a particular chemical is not broken down in the digestive system of organisms, but rather stored, in fats usually. Mercury is an example of another chemical that is know to bioaccumulate. Beyond that, more labile PBDEs, like deca-PBDE, will break down into its more persistent cousins, penta- and tetra (four bromines) -PBDE. PBDEs have also been shown to degrade overtime, using heat and light, to toxic chemicals: polybrominated dibenzodoxins and polybrominated dibenzofurans. So even though they are not acutely toxic, PBDEs may prove to have chronic effects.

The evidence of environmental impact of PBDEs have prompted legislation against them. In Canada there is legislation against PBDE under subsection 93(1) of the Canadian Environmental Protection Act, 1999. In the United States, there is no federal legislation, but many states have bans against PBDEs. The European Union has banned the use of PBDEs.
What I find interesting about the case of brominated flame retardants is that it highlights many of the complexities associated with the problems with the chemicals in our life. These chemicals are not good for the environment, and we shouldn't use them; however, the results of not using flame retardants are equally damaging. Solutions are being researched to find effective flame retardants that are not environmentally damaging. It is important to understand that these materials weren't designed to be damaging or done by "evil scientists in labs who don't care about the environment". They were designed to solve a problem. That problem was the flammability of materials. Unfortunately, they also created a problem. Every action will have a reaction. 

References:
See part one for the references.

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