Alphonse's other hand joins the first, seeing as Toothless just has so much chin to scratch. He's more than happy to soothe that itch, now that he knows the dragon is enjoying it. Oh, he knows it'll be sooner rather than later that he'll get antsy and want to go, and Al has his own interrupted exercise to get back to anyway. But for now, he's taking full advantage of the opportunity.
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