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Sir Keir Starmer has called on Liz Truss not to claim an allowance of up to £115,000 a year that she would be entitled to after resigning as PM.
Liz Truss announced her resignation from the lectern outside No 10 on Thursday after just 44 days in the job.
It means she will now be able to claim the Public Duty Costs Allowance (PDCA), currently set at £115,000, to which all former prime ministers are entitled.
But the Labour leader said she had "not earned the right" to the allowance.
Former prime ministers are able to draw on the PDCA for any costs that arise as a result of public duties.
But Sir Keir, speaking to the BBC, said: "She shouldn't take that entitlement. After 44 days she has not earned the right to that entitlement, she should turn it down."
Liberal Democrat leader Ed Davey has also said she should not claim the money.
He likened the expenses allowance to a "full state state pension", telling LBC radio it was "many, many times" what workers could expect in retirement.
Their remarks follow similar calls from unions and campaigners for the prime minister to turn it down.
What is the allowance?
The PDCA was announced by former prime minister John Major in March 1991 in the wake of Margaret Thatcher's resignation.
It was introduced in order to assist former prime ministers still active in private life, with payments only made to meet the actual cost of continuing to fulfil public duties.
The costs are a reimbursement of incurred expenses for office costs and secretarial costs "arising from their special position in public life" - for example office costs, salaries for staff who help them with their work in public life, or travel to events where they are appearing as an ex-PM.
It is not paid to support private or parliamentary duties, with the fact-checking charity Full Fact concluding it is incorrect to describe the allowance as a salary or pension - or to claim former prime ministers simply "get" the money.
All former prime ministers are eligible to draw on the PDCA. Mr Major, Tony Blair, Gordon Brown, David Cameron and Theresa May have all claimed the allowance after leaving No 10. It is not yet known whether Boris Johnson has claimed the allowance as the most recent annual figures are yet to be published.
The current limit on what they are able to draw is set at £115,000 and has remained frozen since 2011.
Former PMs have not always claimed the full amount, and it is not paid automatically, so they have to provide receipts.
Both Mr Major and Mr Blair claimed the full amount for 2020-21, Mr Brown claimed £114,712, Mr Cameron claimed £113,423 and Mrs May claimed £57,382.
The fund also allows former PMs to claim up to 10% of the cost of this allowance to fund the pensions of staff who work in their post-prime ministerial offices.
There is also a severance payment, which amounts to a one-off payment of 25% of the annual salary for the post that ministers have left. For prime ministers it is about £19,000 (25% of £79,000 annual salary).