By sheer luck I've found the answer to my own question. Flipping through some old issues of The Formation Sign, I found in issue no.86 (April 1972), p.12, that the green over black rectangle was noted being worn by the 2nd London Irish Rifles in August 1941, when it formed part of the 47th Division. It was positioned below a single dark green bar below the divisional sign (Bow Bells). A quick look into Joslin's Orders of Battle showed that the 2nd LIR at the time was in the 4th London (subsequently 140th London) Inf Bde, 47th Div.
Presumably the green over black sign was worn prior to the authorisation of the black on green shoulder title?
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