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When you import or load an epub into Sigil it will automatically grok utf-16 (and many other encodings) and convert it to utf-8 which is now an industry standard. The problem with any other utf- encoding is that they are endian dependent (little vs big endian). So you would need to specify either utf-16 little or utf-16 big and then use the appropriate Byte Order Mark (to indicate endianness).
There is no such thing as characters above the utf-8 code point encodings. Utf-8 can represent the full range unicode codepoints.
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