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Hilbert–Schmidt (HS) decompositions and Frobenius norms are used to analyze biseparability of 3-qubit systems, with particular emphasis on density matrices with maximally disordered subsystems (MDS) and on the W state mixed with white noise. The biseparable form of a MDS density matrix is obtained by using the Bell states of a 2-qubit subsystem, multiplied by density matrices of the third qubit, which include the relevant HS parameters. Using our methods, a sufficient condition and explicit biseparability of the W state mixed with white noise are given. They are compared with the sufficient condition for explicit full separability given in a previous work.