Ozone, a special form of oxygen that screens out harmful

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Ozone, a special form of oxygen that screens out harmful ultraviolet rays, reaches high concentrations twelve miles above Earth, where it has long appeared that it was immune from human influence; we have now realized, though, that emissions of industrial chlorofluorocarbons deplete the ozone layer.

(A) has long appeared that it was immune from
(B) has long appeared to have been immune from
(C) has long appeared as being immune to
(D) had long appeared immune to
(E) had long appeared that it was immune to

[spoiler]OA: Please discuss on two things

1. is immune from a correct idiom????? though immune to I am aware
2. Tense in option D[/spoiler]

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