A method for transferring a liquid sample from a primary liquid stream to a secondary liquid stream for analysis of the liquid sample in the secondary liquid stream, said method comprising: (a) providing a liquid sampling valve having: (i) a stator with a stator face, a primary stator passage extending along a primary path through said stator and opening to said stator face, an inlet secondary stator passage extending along a secondary path through said stator and opening to said stator face, an outlet secondary stator passage extending along the secondary path through said stator and opening to said stator face, said inlet and outlet secondary stator passages being fluidly connected in said stator by a secondary bypass channel, an inlet discharge passage extending along a discharge path through said stator and opening to said stator face, and an outlet discharge passage extending along the discharge path through said stator and opening to said stator face; and (ii) a rotor having a rotor face in fluid-tight contact with said stator face at an interface, said rotor face including a shuttle; (b) delivering the primary liquid stream along the primary path through said primary stator passage to fill said shuttle with the liquid sample; (c) rotating said rotor in a first circumaxial direction about an axis of rotation to bring said shuttle into fluid communication with said inlet and outlet secondary stator passages, and out of fluid communication with said primary stator passage; (d) delivering the secondary liquid stream along the secondary path to transport the liquid sample with the secondary liquid stream out from said shuttle through said outlet secondary passage; (e) further rotating said rotor in said first circumaxial direction about said axis of rotation to bring said shuttle into fluid communication with said inlet and outlet discharge passages, and out of fluid communication with said inlet and outlet secondary stator passages; (f) performing a discharge operation along said discharge path to transport the secondary liquid out from said shuttle through said outlet discharge passage; and (g) further rotating said rotor in said first circumaxial direction about said axis of rotation to bring said shuttle into fluid communication with said primary stator passage. (a) providing a liquid sampling valve having: (i) a stator with a stator face, a primary stator passage extending along a primary path through said stator and opening to said stator face, an inlet secondary stator passage extending along a secondary path through said stator and opening to said stator face, an outlet secondary stator passage extending along the secondary path through said stator and opening to said stator face, said inlet and outlet secondary stator passages being fluidly connected in said stator by a secondary bypass channel, an inlet discharge passage extending along a discharge path through said stator and opening to said stator face, and an outlet discharge passage extending along the discharge path through said stator and opening to said stator face; and (ii) a rotor having a rotor face in fluid-tight contact with said stator face at an interface, said rotor face including a shuttle; (i) a stator with a stator face, a primary stator passage extending along a primary path through said stator and opening to said stator face, an inlet secondary stator passage extending along a secondary path through said stator and opening to said stator face, an outlet secondary stator passage extending along the secondary path through said stator and opening to said stator face, said inlet and outlet secondary stator passages being fluidly connected in said stator by a secondary bypass channel, an inlet discharge passage extending along a discharge path through said stator and opening to said stator face, and an outlet discharge passage extending along the discharge path through said stator and opening to said stator face; and (ii) a rotor having a rotor face in fluid-tight contact with said stator face at an interface, said rotor face including a shuttle; (b) delivering the primary liquid stream along the primary path through said primary stator passage to fill said shuttle with the liquid sample; (c) rotating said rotor in a first circumaxial direction about an axis of rotation to bring said shuttle into fluid communication with said inlet and outlet secondary stator passages, and out of fluid communication with said primary stator passage; (d) delivering the secondary liquid stream along the secondary path to transport the liquid sample with the secondary liquid stream out from said shuttle through said outlet secondary passage; (e) further rotating said rotor in said first circumaxial direction about said axis of rotation to bring said shuttle into fluid communication with said inlet and outlet discharge passages, and out of fluid communication with said inlet and outlet secondary stator passages; (f) performing a discharge operation along said discharge path to transport the secondary liquid out from said shuttle through said outlet discharge passage; and (g) further rotating said rotor in said first circumaxial direction about said axis of rotation to bring said shuttle into fluid communication with said primary stator passage.