It's likely prostatic fluid or precum. Erections, ejaculations and orgasms are actually separate, it's just that for the vast majority of men they happen together. A man can orgasm without an erection, and can orgasm without ejaculating.
Does his orgasm feel penile or has he mentioned any feeling coming from his prostate or anal area? Perhaps even full body?
You mention that he tightened up. I wonder if he strongly contracted his pelvic floor muscles (BC for males, often called PC in general) causing pressure on his prostate and triggering the orgasm.
Might I ask, how you were playing with him? Was it penile stimulation?