German interior ministry spokesman Tobias Plate said that most of the arrivals expected Monday would be families with children, putting the number in the "double-digit range".
Under the scheme agreed with the EU last month, one Syrian refugee will be settled in Europe legally in return for every migrant taken back by Turkey from EU member Greece.
With uncertainty surrounding the returns, tensions flared in Greek refugee camps, just as Amnesty International accused Turkey of illegally forcing groups of Syrians to return to their conflict-torn country.
Police used stun grenades to restore calm during the late-night fight -- the second such incident within two days in Greece -- which caused serious damage to the island's Vial camp, including the medical dispensary, state ANA news agency said.
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Medical charity Doctors of the World (MDM) said it had pulled out of the camp to protect its staff.
"The dispensary was almost entirely destroyed and security was no longer sufficient," MDM spokesman Evgenia Thanou told AFP.
Around 700 refugees and migrants today were heading towards another camp in the main town of Chios under police escort, state TV ERT said.
Meanwhile Amnesty said that the alleged forced repatriation of Syrians showed the "fatal flaws" in the migrant deal agreed with the European Union.
The rights group said its research in the south of Turkey suggested the country was forcing around a hundred Syrians to return home on a daily basis.