Westminster City Council is naming and shaming offices
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Among the worst culprits are the Department for Education and Skills, the Department for Trade and Industry and the Department for Environment, Food & Rural Affairs.
The council said it has contacted the departments to ask that they tackle the problem, which is being highlighted to mark National No Smoking Day.
The Home Office was praised for keeping the surrounding area tidy by providing bins for smokers, and the Department of Health also keeps the front of its building free of litter.
The council has the power to issue £80 fixed penalty notices to people caught throwing cigarette butts on the ground or in drains. The fine is reduced to £50 if paid within 10 days.
The maximum court fine for a littering offence is £2,500.
In the most serious cases, local authorities can issue Street Litter Control Notices which give premises 28 days to tackle the issue of litter or face legal action.
Defra is currently looking at extending the powers of the control notices to take into account the smoking legislation.
Westminster City Council's cabinet member for street environment, councillor Alan Bradley, said: "The smoking ban is fast approaching and it is imperative that organisations take steps now to tackle the problem of smokers casually throwing their cigarette butts and other waste on the pavement outside their buildings.
"It is terribly harmful to the reputation of our city if visitors are confronted by the sight of cigarette waste on our pavements."
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