In the first query, you need single quotes around '$email', while in the second query you need to remove the quotes around NULL (it's a SQL keyword, not a string literal). In any case you can save yourself a query by making the email column unique in the DB table, then just do the insert and check for a duplicate key error. (Regarding the NULL, you don't even need that in the insert, just leave out that column.)
// mysql connection stuff, then...
$email = mysql_real_escape_string($_GET['email']); // *always* sanitize user inputs to SQL
$sql = "INSERT INTO newsletter (email) VALUES('$email')";
$result = mysql_query($sql);
if($result == false)
{
if(mysql_errno() == 1062) // duplicate key error
{
echo "Email allready subscribed to Newsletter";
}
else
{
error_log(mysql_error()."\n$sql");
echo "Sorry, there was a database error which has been logged for the SysAdmin to look at.";
}
}
else
{
echo "Done.";
}