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Do you normally park up hill or down? If up hill, the rear sun roof drains may be clogged. This is rare as the drains are in the "C" pillars area, but can be easily checked by pouring a cup of water into each side of the SR channel and watching for water to drain out by the rear wheel.
On a side note, the odor could be coming from the engine compartment. If found this oddity:
"Hi all, I have a 06 XC90 and have always had the odor in rain or after I wash the truck. I confirmed my sunroof drains were all working fine and my AC drips like crazy under the truck when idling. So, by accident while cleaning my wiper blades I spilled bleach in down the windshield into the black part of the trim that the windshield connects to. I had a puddle of nastiness and ran water over it to avoid damaging anything. I started the truck and got a blast of bleach scented air and noticed the usual mold odor was gone. So, I waited a week and still nothing. I washed the truck again and with no bleach, the odor returned. So, I took an oil funnel and poured bleach into the openings near the windsheild (I think these are drains or air intakes) and immediately the odor is gone. I'm at 5 weeks with a few washes and rain and still no odor. If it returns, I'll put a few more drops of bleach in."
Strange. Be very careful with bleach, always dilute it with a 10:1 water ratio. Straight bleach is a no no!
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Keeping it running is better than buying new
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