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In LightRoom , a PNG w/ transparency will be previewed & exported to JPEG w/ transparency replaced by pure white.
I'd like it replaced by pure black instead. Is this possible, or do I have to go into PS?
Yes you will need Ps (TBMK)
Relatively easy though- (using my method. There are other ways!!)
1) Select the PNG in LrC and
2) [Ctrl + E] to edit the PNG in (installed) Photoshop
3) Add a new layer and drag it below the PNG layer
4) Fill the new layer with Black.
[Ctrl + Backspace] will fill the new layer with the Background color swatch. eg. a red background swatch will fill with red.
5) The new background black layer will show through transparent pixels.
6) [Save as Copy] to obtain a flattened JPG file.
Import the new JPG to the LrC catalog by 'Import' or a 'Folder Synchronize'.