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A further 120,000 refugees will be relocated around Europe, ministers agreed today.
The decision follows an earlier accord to redistribute 40,000 from Italy and Greece but the Luxembourg government gave no details on how they would be shared out across the bloc.
Several states firmly oppose proposals to distribute refugees around Europe according to national quotas.
Visiting young Syrian refugees in Jordan and Lebanon today, in camps supported with British money, David Cameron urged other EU countries to give more aid money to improve conditions.
He told ITV News that caring for refugees in these camps is the best thing for all concerned.
"It's now time for other countries to step up and join us doing even more because if we don't spend that money, many, many more people will make that potentially lethal crossing to Europe and lives will be lost," he said.
ITV News' Senior International Correspondent John Irvine reports:
At least 20 people have been killed in one of two car bomb blasts in the eastern Syrian city of Hasaka, state television reported.
One of the explosions reportedly occurred in the north of the city, and the other in its centre.
A dedicated government minister will be appointed to oversee Britain's intake of 20,000 Syrian refugees, David Cameron has announced.
Richard Harrington will ensure the new arrivals are given a "warm welcome" to the UK, he said.
During a visit to a refugee camp in Lebanon, the Prime Minister said Britain was already the second largest donor to camps in the region - and vowed to pump more money into schemes such as education for the children affected by the conflict in Syria.
He said he wanted to take in people directly from the camps to try to discourage them from paying traffickers and making the dangerous journey across the Mediterranean.
Prime Minister David Cameron has arrived in Beirut to visit refugee camps in Lebanon, which are housing more than a million people fleeing violence in Syria.
He toured the Bekaa Valley settlement, less than a mile from the Syrian border, meeting those affected by the war in the neighbouring country and seeing the conditions they face, as well as seeing how aid sent by Britain is being used.
Lebanon will receive £29 million of the extra £100m pledged by the UK to help with the refugee crisis, which will pay for food packages, clean water, blankets, stoves, mattresses, counselling and play areas for children.
He met a family who are due to be flown to the UK as part of a relocation scheme, following his announcement last week that Britain would take in 20,000 refugees over the next five years.
He was also invited into the tent of a Syrian mother who told him of their fight for survival - revealing she had just five dollars a month to keep and feed her 10 children.
Later, he will visit his Lebanese counterpart Tammam Salam to discuss the refugee crisis.
Germany has halted rail traffic arriving from Austria according to a spokeswoman for Austrian rail company OeBB, quoted by the Reuters news agency, and has reintroduced border controls.
The situation in the other direction - from Germany to Austria - was not immediately clear.
German newspaper Bild also reported on Sunday the authorities were planning the temporary reintroduction of border controls in response to the refugee crisis.
Germany is now reaching its limit on its ability to take in more refugees, a senior minister has warned as thousands of people continued to arrive in the country over the weekend.
In an interview with Der Tagesspiegel newspaper, the country's Economy Minister Sigmar Gabriel criticised his counterparts across Europe for a lack of action on the issue.
Around 13,000 arrived in Munich alone on Saturday, and the country expects 800,000 new arrivals by the end of the year.
"It's true: The European lack of action in the refugee crisis is now pushing even Germany to the limit of its ability," Mr Gabriel said.
Latest ITV News reports
On a visit to Jordan, David Cameron says that the EU must "follow Britain's lead" and fund more refugee camps around Syria.
The prime minister has insisted the UK will not participate in plans to redistribute 160,000 refugees who have arrived in Europe.