As promised, the rest of my impressions of chap 22 to 36:
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The Road so far...
(*Insert 'Carry on my Wayward Son' in the background*)
If I have to name the 'main character' of this volume, it would have to be the 'Kihara Family'. Just like how the 'main character' of volume 3 is the 'United States'. We learn alot more about the Kihara as a whole in this volume than any before, while individually we get two separate backstories on two of them. Kihara Kagun is probably a character that is a long time in the making, simply put you don't have a family made up of the scums of the Earth without at least one of them growing a conscience. I like Enshuu's backstory because it wasn't a sob story about her getting kidnapped and imprisoned, it was actually a horror story of how you cannot contain a Kihara.
I still have no idea what did Shuri do to Sigyn... And how did Utgard-Loki get knocked out by an illusion 
?
I said before that the main character of volume 4 is the Kihara Family, but if I had to pick a protagonist for this volume it would be Maria. Ever since she appeared, she's been taking the spotlight for most of the scenes, primary because she's the most knowledgeable of three girls when it comes to Supernatural abilities. She displayed an almost Kamijou-like quality with how she could infer Marian's capabilities through her actions even though this is the first time she's fighting a Magician, at the same time there's that lecture she gave to Enshuu as she delivered a long awaited beat-down... Btw, on hindsight, I guess it should have been obvious that there's no way Enshuu was actually becoming those characters she had named 
But it was funny when Enshuu tried to use Kamijou Touma's thought pattern and Maria countered by saying that might only scare her sister
Everything comes full circle with the connection between Maria-Kagun-Marian, which once again on hindsight, the student-teacher relationship between Maria and Kagun should have been obvious The lovers relationship with Marian on the other hand was not expected Since her introduction Marian has been depicted as this cruel, unstoppable monster, to have her rage like this over one person was something I didn't expect to see 
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Okay, I'm also going to need a full explanation about the whole alter-dimension thingy because I get the feeling this isn't going to adapt well in the Anime
And now my favourite moment, Maria probably spent the entire volume hearing Kamijou's name being thrown left and right, she herself probably knows a few things beforehand but didn't think much about them. But then to see him in person and actually living up to the rumours that she had heard (I blame it partly on how the narrative hyped it up ) that must have been quite emotional for her. Kamijou on the other hand shows his leet Paragon skills as he persuaded Marian from ending the world, and it looks like his observation skills have improved sharply as well.
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This time it took me thirty minutes to write this