An Italian coast guard ship that took aboard some of the Aquarius's passengers to make the trip safer arrived soon after dawn in the eastern Spanish port, where a staff of 2320, including volunteers, translators and health officials, awaited.
Doctors Without Borders, known by its French acronym MSF, tweeted that migrants on board the Aquarius had been "calm and pleased" to hear they would be arriving in Spain on Sunday morning.
Spain has "opened its arms at a time when many reject (refugees) and are not showing solidarity", Elhadj As Sy of the International Federation of Red Cross and Red Crescent Societies told AFP in the Spanish port of Valencia, where he was overseeing the arrival of 630 migrants from the Aquarius rescue boat.
The Aquarius itself is due to dock once all the migrants are off the Italian vessel.
Salvini, whose unashamedly xenophobic rhetoric formed a key part of his party's election campaign, appears determined to make the migration question his main priority even if Italy's denial of a safe harbour to the Aquarius this week sparked worldwide outrage.
After Spain invited the Aquarius to land, Italy sent the Dattilo and Orione to help transport the migrants.
At the port, a huge banner was hung up saying "Welcome home" in various languages including Arabic.
On Saturday, the Spanish government announced it will transfer to France any migrants arriving on the convoy who express a desire to reach that country.
Among the passengers are 450 men and 80 women - at least seven of them pregnant - as well as 89 adolescents and 11 children under the age of 13, figures released by the Valencian authorities show.
A total of 630 of migrants had been rescued by the Aquarius, a rescue ship operated by Doctors Without Borders (MSF) and SOS Mediterranee, last weekend off the coast of Libya.
The arrival came after Spain's Foreign Minister Josep Borrell agreed the migrants could go there "to oblige Europe to forge a common policy to a common problem". The asylum seekers were eventually accepted by Spain, whose new Prime Minister Pedro Sanchez said taking them in was a humanitarian obligation.
Journalist Jaime Velazquez has the latest from Madrid.
The plight of the Aquarius has again highlighted the failure of European Union member states to work together to deal with the influx of migrant arrivals since 2015.
French President Emmanuel Macron and new Italian Premier Giuseppe Conte meet Friday amid tensions between the two countries over migration. Spain's first task will be to ascertain the condition of the arriving migrants and then examine each of their individual situations case by case, Valerio said.
Italy's new populist government is criticizing aid groups that rescue migrants in the Mediterranean Sea, declaring two German rescue boats can't dock in Italian ports even though the groups operate at sea and don't bring migrants ashore. "I hope that they can continue and do more and that other countries will follow suit as well", he said.
"Two other ships with the flag of Netherlands, Lifeline and Seefuchs, have arrived off the coast of Libya, waiting for their load of human beings abandoned by the smugglers", Matteo Salvini, the leader of the anti-immigrant party the League, wrote on his Facebook page. It also recovered four bodies and declared another 43 people missing at sea.
Almost 1,000 migrants arrived Friday and Saturday in the south of Spain, the third busiest gateway for migrants into Europe after Italy and Greece.
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