The only 'Line Color' option that are accessible by right-clicking on a picture and choosing 'Format Picture', are: No line;Solid line; Gradient line. A specific colour isn't available until you choose, say, 'Solid line'; the default for that is theme-related; for the default theme, it's a pale blue and the default for any given theme can't be changed.

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Cheers,
Paul Edstein
[Fmr MS MVP - Word]