In <your zen cart path>/includes/modules/attributes.php, you will find the following block of code (in around line 200):
if ($_SESSION['cart']->contents[$prod_id]['attributes'][$products_options_names->fields['products_options_id']] == $products_options->fields['products_options_values_id']) {
$selected_attribute = $_SESSION['cart']->contents[$prod_id]['attributes'][$products_options_names->fields['products_options_id']];
} else {
//$selected_attribute = false;
// JEFF - fix for default attribute:
$selected_attribute = ($products_options->fields['attributes_default']=='1' ? true : ($products_options->RecordCount() == 1 ? true : false));
}