In Drupal 6, Profile module stores taxonomy values for users with this format:

a:3:{s:17:"Local Development";s:17:"Local Development";s:35:"Environmental Policy and Management";s:35:"Environmental Policy and Management";s:22:"Environmental Research";s:22:"Environmental Research";}

Is there a way to programmatically convert that to an array using PHP and/or Drupal 7 functions?

This is the array I would like to obtain:

Local Development
Environmental Policy and Management
Environmental Research

The drupal stores the users data in serialized format to get it in array format you can use
unserialize ( string $str [, array $options ] ) function in php.

here is the example for you to get better understanding PHP : unserialize() function

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