Police were tracking the group’s dealings for four years before launching “Operation Plastic Free on Thursday.
Investigators found that the smuggling ring was headed by Claudio Carbonaro who was “responsible for atrocious crimes in the 1980s and 1990s, including over 60 murders.”
Carbonaro briefly become a police witness, before returning to Sicily in 2013, where police say he became head of the historic Carbonaro-Dominant clan. Police believe he had been planning the move while in protective custody.
Ragusa Police Commissioner Salvatore La Rosa told media that Carbonaro had overseen a rebuilding of mafia strength in the region.
The scheme was uncovered when shoes containing the toxic plastic were discovered being sold in Rome.
Police say the group would also illegally disguise the sludge created by the washing of the plastics, which are made up of a harmful combination of soil mixed with fertilizers and pesticides.
The waste was buried and covered with cement and asphalt in land scattered across the region of Vittoria, creating serious environmental damage.
The group, police said, also profited from not having to pay for the proper disposal of toxic materials.
Officials say the suspects went to violent lengths to protect their business, including setting rival company trucks on fire and threatening competitors with weapons.
Police also seized five companies - believed to have been used to traffick the toxic waste - which had annual turnovers of more than five million Euros.
Ten of those arrested are in pre-trial detention, while five remain under house arrest.