Tourists queued for the ferry after flights to and from the Spanish island were cancelled amid smoldering skies.
Scientists said another volcanic vent opened up, exposing islanders to possible new dangers.
The Cumbre Vieja volcano began erupting on September 19 and has intensified in recent days, prompting the evacuation of three additional villages on La Palma.
The island is part of Spain’s Canary Islands archipelago in the Atlantic Ocean off northwest Africa.
Almost 7,000 people have been forced to abandon their homes.
The huge ash cloud is an immediate concern for residents as it rises from the volcano and is carried by the wind to other parts of the island.
Local government has urged residents in affected areas to avoid going outside and only do so wearing masks and goggles.
In addition to being a significant danger to planes, the ash can cause damage to people’s airways, lungs and eyes.
The recent volcanic eruption is the first since 1971 on La Palma, which has a population of 85,000.La Palma Airport operator Aena said the airport was “inoperative” due to the accumulation of ash.
Other airports in the Canary Islands were still operating Saturday but some airlines were suspending flights, Aena said.
Rivers of lava have been sliding down the mountainside toward the southwestern coast of the island, destroying everything in their path including hundreds of homes.
Emergency crews pulled back from the volcano on Friday as explosions sent molten rock and ash over a wide area.
The speed of the lava flow has slowed down considerably and the lava is now barely moving forward, with about 1.2 miles left to reach the sea, said Miguel Angel Morcuende, head of the Canary Island Volcanic Emergency Plan.
He added: “I don’t dare to tell you when it’s going to get there, nor do I dare to make a forecast.”
Watch: Aerial footage shows charred land surrounding La Palma volcano