Valve assemblies are described that provide segmented shuttle of liquid into sample vessels and automatic mixing via bubbles in the segmented liquid. A valve assembly includes a first valve member having ports configured to receive a pressurized gas, a first fluid, and a second fluid. The valve assembly also includes a second valve member coupled adjacent to the first valve member. The second valve member comprises a plurality of channels configured to interface with the first valve member. In a first configuration, the first fluid is loaded into an external loop. In the second configuration, the second fluid is eluted from the column into a vial in a segmented stream via bubbles of pressurized gas. Bubbles of gas automatically mix the eluted sample fluid.