Methane.
http://aetinc.biz/newsletters/2010-insights/october-2010
Methane gas is relatively non-toxic; it does not have an OSHA PEL Standard. Its health affects are associated with being a simple asphyxiant displacing oxygen in the lungs. Miners previously placed canaries in deep mines to check methane gas levels. Reportedly, canaries keeled over at about 16% oxygen indicating it was time to leave.
Methane is extremely flammable and can explode at concentrations between 5% (lower explosive limit) and 15% (upper explosive limit). These concentrations are much lower than the concentrations at which asphyxiant risk is significant.
Your world has an unstable atmosphere of 15% oxygen, 84% methane, and 1% (and rising) CO2. Oxygen is 10% so at the very low end of what humans need. Unstable because the methane does consume the oxygen and vice versa. The world is in flux - a methane world which terraformers seeded with photosynthetic algae in the recent past. Oxygen is being rapidly produced by the greening oceans of this world. Explosions happen but are rare - there is too much methane to easily explode.