It was probably just dirty litterbox issues, but if it continues I would take her to the vet. Cats will go outside the litterbox to let you know something is wrong (i.e. she's in pain or isn't feeling right). Hopefully it's just an isolated incident.
Ratbastid said it - try Nature's Miracle or a 50:50 white vinegar/water mixture to scrub the stain out.
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Kim
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