The new charge in London from October 23 is additional to the congestion charge of £11.50 that vehicles need to pay every day to enter the city's central zone.
"It's staggering that we live in a city where the air is so toxic that many of our children are growing up with lung problems", said mayor Khan in a statement. "If we don't make drastic changes now we won't be protecting the health of our families in the future".
He said the T-charge was the "toughest emission standard of any major city" and was overwhelmingly backed by Londoners because they wanted immediate action to tackle air pollution.
London Mayor Sadiq Khan said the "toxicity", or "T-charge", is essential as he announced his latest effort to crack down on pollution in the capital.
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Under the proposals, the owners of diesel and petrol vehicles manufactured before 2005 that do not meet Euro 4 emissions standards for nitrogen oxide (NO2) and particulates will be required to pay.
The new levy means that anyone driving the most polluting cars will face a charge of £21.50 a day to drive into central London during weekdays. He explained that the introducing the T-Charge over an extended area of the capital "will be a much bigger issue for many more London road users than if it had just been in a central area".
In total, more than 37 stakeholders and organisations - including numerous councils, Global Action Plan and the Licensed Taxi Drivers Association - support the principle of the T-Charge, which uses cameras as monitoring and enforcement measures.
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The crack-down is set to be the toughest emission standard of any world city, affecting the vast majority of pre-2006 vehicles.
Both charges will apply Monday-Friday from 7am to 6pm.
The charge is a step to bringing in the world's first "ultra-low emission zone", which will charge more polluting cars.
"I will continue to do everything in my power to help protect the health of Londoners and clean our filthy air", Khan added. We are pleased the Mayor has prioritised improving air quality.
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