Use the options in the Boundary tab > Selection panel > Type list to specify how segments in the active boundary are selected:
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Select All — Click to select all segments of the boundary (they turn yellow).
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Deselect — Click to deselect any selected boundary segments (they turn white).
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Invert Selection — Select to deselect the part of the boundary that is currently selected and select the part of the boundary that is currently unselected.