have a look at the mysql docu on insert-on-duplicate From there you can see that you can use something like this:
INSERT INTO table (a,b,c) VALUES (1,2,3),(4,5,6)
ON DUPLICATE KEY UPDATE c=VALUES(a)+VALUES(b);
in your case:
INSERT INTO accounting_positions
(`date`, `customer`, `type`, `product`, `volume`, `payout`, `count`)
VALUES
('2012-01-10','10','regular','60sec',65,83,13),
('2012-01-10','10','regular','binary',15,83,13)
ON DUPLICATE KEY UPDATE volume=volume+VALUES(volume);
which would add the new and the old value. If you only want the given insert value to overwirite the row then do: ON DUPLICATE KEY UPDATE volume=VALUES(volume)