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Empowerment is the process by which you increase item level. When you empower an item, you sacrifice 1-5 other items and pay anima shards to add experience to that item. Those items will be completely destroyed and, other than adding item experience, will not affect the item you are empowering in any way.
Fusion is the process by which you increase item rarity (color). This is done by taking two same-type max-level items (or one item and a catalyst) of a certain rarity and "combining" them into a level 1 item of better rarity.
What items are compatible for fusion?
Glyphs and Signets are upgrade components that can be slotted into gear to provide bonuses and effects. This can be done via the fusion tab, at no cost. You may destroy a slotted glyph or signet for free, but removing one without destroying it costs Marks of Favor based on the glyph or signet's rarity. Unlike weapons and talismans, glyphs and signets max out at level 20, regardless of rarity. They also have different experience requirements.
Your item might just be at it's max level for the rarity.
So, if you're trying to add XP to your green item that is already level 20 or blue item that is already 25, it won't let you do it.
virpyre went to far more effort to list the mechanics of the system in detail.