The flow dynamics of veins and arteries differ.
If colour flow is available it can be utilised to determine this. With the probe angled so that flow is either marginally towards or away from the probe, the colour flow convention is:
Blue = Away
Red = Towards
This is easily remembered by the acronym B.A.R.T.
This image demonstrates a groin A-V fistula, showing the value of colour flow. Click the image to see a larger version.