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The vaccines will be administered by appointment at three central hubs located at Westmead, RPA and Liverpool hospitals, Ms Berejiklian confirmed on Wednesday morning.
Anyone who receives the vaccine will need a second dose a few weeks later.
NSW Chief Health Officer Kerry Chant said the priority was to protect workers at greatest risk of coming into contact with the virus.
An estimated 10,000 to 15,000 workers across the quarantine system will be covered in the first three weeks. The balance will target other health workers.
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“We think this is a healthy number to have vaccinated in the next three weeks to cover us, but obviously the more you do, the better,” Ms Berejiklian said.
Quarantine workers - including nurses, doctors, police officers, security guards, and cleaners - would be the first to receive their initial dose of the Pfizer vaccine, followed by healthcare workers whose work puts them at risk of being exposed to the virus.
From Friday, NSW will revert to the two-square-metre rule for indoor and outdoor events and masks will only be compulsory on public transport and in taxis and Ubers.
Australian governments lift safety restrictions despite COVID-19 dangers and vaccine doubts
Australian governments are continuing to scrap health and safety restrictions and promote the back-to-workplaces drive of big business, rather than maintain even limited measures to curb further COVID-19 outbreaks before the population can be immunised on a broad scale.
No vaccinations have yet occurred in Australia, and fresh doubts exist about the availability, timing and efficacy of the vaccines ordered by the federal government. Clear dangers still exist that more infections will escape from hotel quarantines for international arrivals, including cases of the more infectious mutant variants spreading around the globe.