My bad, yeah. I was actully testing it on Wound Poisons several days ago (because I was similarly puzzled by the numbers).
Looking through the generated log for Rogue_23_05_43 it looks like Envenom is not proccing instant poison at all.
32.79 Rogue_T8_23_05_43 schedules execute for envenom
32.79 Rogue_T8_23_05_43 performs envenom
32.79 Rogue_T8_23_05_43 envenom hits Fluffy Pillow for 10943 nature damage (crit)
32.79 Rogue_T8_23_05_43 gains 25 (25) energy from relentless_strikes (35)
32.79 Player Rogue_T8_23_05_43 loses Combo Points (5)
32.79 Player Rogue_T8_23_05_43 gains Combo Points (1)
32.95 Rogue_T8_23_05_43 performs melee_main_hand
The last envenom was performed at 31.49 so the buff is there.
SnD is also not proccing it (though I'm not really sure if it actully does, I believe it does)
22.30 Rogue_T8_23_05_43 schedules execute for slice_and_dice
22.30 Rogue_T8_23_05_43 performs slice_and_dice
22.30 Rogue_T8_23_05_43 gains 25 (25) energy from relentless_strikes (60)
22.30 Player Rogue_T8_23_05_43 loses Combo Points (5)
22.49 Rogue_T8_23_05_43 performs melee_main_hand
The last envenom was performed at 19.54
Though it does proc off rupture
47.31 Rogue_T8_23_05_43 schedules execute for rupture
47.31 Rogue_T8_23_05_43 performs rupture
47.31 Rogue_T8_23_05_43 gains 25 (25) energy from relentless_strikes (75)
47.31 Player Rogue_T8_23_05_43 loses Combo Points (5)
47.31 Rogue_T8_23_05_43 performs instant_poison
Also, the first envenom is performed 6.97 seconds into simualation. That's basically ~2 hemos, 2 finishers and a couple melee swings without the buff.
As a diclaimer: the log was done with a 3.2 speed mainhand, 1500 hit rating and 500 expertise rating. So basically each swing/ability under envenom buff should've procced mh poison.