The manual is useless: "Tour of Settings/Sound/Sound Out: Optical: You can connect an audio device that supports Optical to the optical digital audio output port to enjoy your TV’s sound in richer quality and greater convenience. Only available for models with an optical digital port. For some devices, you can adjust the volume using the TV remote control."
So do you have one of those "some" devices? The answer is simple: try it! If it lowers the volume, then it lowers the volume. If it doesn't lower the volume, then it doesn't lower the volume. [[I'm such a sphinx. Or maybe that's Yogi Berra.]]
[Speculation follows, YMMV: I would expect that it does not have variable volume out over optical, because that would involve more processing in the TV. I also believe that you have turned off as much processing as you can, by setting "Sound/Additional Settings/Digital Sound Out" to "PCM". Typically, optical-out is transmitted "raw" from the decoder and not post-processed. (I believe this custom is because original use was primitive: digital out on DAT & CD machines, just very simple bitstream re-routing to SPDIF over TOSlink.) Also typically, TVs which *do* any processing on the audio cause delays and then have problems with video/audio sync. So be grateful: unless you really love the LG remote, it's good that you can control the volume using the Core, instead.]