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Unions must ensure there will be "sufficient" staffing during this week's ambulance strike to protect patients, the health secretary says.
Workers in England and Wales will walk out on Wednesday in a dispute over pay, but life-threatening emergencies will be responded to.
Unions say discussions were still taking place with ambulance trusts to draw up detailed plans for cover.
Steve Barclay said there is a lack of clarity about what is being offered.
He said it was for the unions to ensure they "meet their obligations" for emergency cover so that people in crisis get the care they need.
But unite leader Sharon Graham, whose union is co-ordinating the ambulance strikes with Unison and GMB, said Mr Barclay will "have to carry the can if patients suffer".
"It's Steve Barclay who is holding the country to ransom," she told the Daily Mirror.
Unions say the government have the power to stop the ambulance strike - and action by nurses on Tuesday - if it signalled a willingness to discuss pay.
The ambulance walkouts will involve paramedics as well as control room staff and support workers.
The action by the three main ambulance unions - Unison, GMB and United - will affect non-life threatening calls, but those who suffer trips, falls or other injuries may not receive treatment.
Members of GMB are set to follow up the action with another walkout on 28 December.
The government's emergency Cobra committee will meet this morning to discuss how to lessen the impact of the ambulance strike. Ministers have already announced members of the military will on standby to help out.
The unions representing NHS workers have asked for above-inflation pay rises for staff.
The governments in England and Wales have given staff an average rise of 4.75%, with a guaranteed minimum of £1,400.
Mr Barclay has said the government's pay award met the requirements of the recommendations of the independent NHS Pay Review Body and what was being asked for was "unaffordable".
While visiting an emergency call centre in Chelmsford on Sunday, Mr Barclay declined to be drawn on reports the government had ruled out a one-off payment for NHS workers to break the strikes deadlock, saying discussions between his department and the prime minister on the issue were private.
He added: "But I'm keen to continue a dialogue with the trade unions because there's a range of issues that matter to staff," he said, referring to issues such as technology and safety.
Both Unison and the Royal College of Nursing (RCN) union have threatened further strikes in the new year if an agreement is not reached.
Unison's health of health Sara Gorton urged Mr Barclay to "do the right" thing both for NHS workers and patients and "host genuine talks and put a better pay offer on the table".
"Ministers should take their heads out of the sand, stop pretending they can't boost wages and stop ignoring a worsening staffing crisis," she said.