Hundreds of people are killed on the roads each year, says the ALG
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Drivers who block yellow box junctions or go the wrong way up one-way streets are being warned to expect a £100 fine.
Transport for London (TfL) and councils say they are using new powers to tackle "dangerous and illegal driving".
Traffic-monitoring cameras will be used to spot infractions - such as ignoring "no right turn" signs - in an effort to keep traffic moving.
Drivers can appeal, as they would against a parking ticket, and fines drop to £50 if paid within 14 days.
Six London boroughs are beginning a nine-month pilot scheme from Monday.
It follows the London Local Authorities and Transport for London Act 2003 allowing TfL and councils to enforce some regulations - usually the preserve of the police.
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These new powers will help make roads less congested
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Traffic wardens will also be able to issue fines but TfL says the powers will largely be enforced using existing cameras.
As they are monitored, operators will be able to use their discretion for circumstances such as drivers having to make way for vehicles on 999 calls.
Camden, Ealing, Newham, Croydon, Hammersmith and Fulham and Wandsworth are the six boroughs taking part in the trial.
Councillor Phillip Portwood, of the Association of London Government, said hundreds of people are killed on London roads each year.
He said: "These new powers will help us to [make roads safe] and will also help make roads less congested.
"No-one should believe they have the right to break the law, which is there to protect people. A simple way of not getting a fine is not to break the law in the first place."