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Aveline's companion quest is a fairly long affair, but it will help her gain some status in the guard and net you a fair reward and some good gear.
I suggest that you make sure that you have good equipment and a few levels under your belt before you commit to the fight. The ambush is fairly difficult to survive, if you aren't ready for it. You'll need to face down a lot of raiders, and a raider assassin at once.
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The Way It Should Be - Finding the Ambush Site
Leave an area in Kirkwall and signal that you want to go to Sundermount with the button on the bottom right. There should be a spot marked for the ambush site, if Aveline is in your party. Go there and start moving forward. The first group has a few archers and an assassin. Have someone take out the archers while the other tries to distract the assassin. The assassin will run around the battlefield and do backstabs for a lot of damage, so don’t let anyone get too low for health. Other than that, just keep them away from Varric and your Mage and it won’t be too hard.
As a side note, Varric’s hail of arrows is incredibly nice for wearing away at archers and other fighters in a tight battlefield.
Move up the back road and engage the first small group. Once they go down, another group lead by a reaver will spawn. Have someone take out the archers and have your tank tie up the reaver. Grind away at this heavy hitter until he dies, and loot the body.
Move on and grab the chest and the elfroot by the road, then move along to the next open area for another fight with some archers and assassins. Repeat the usual tactics to take them out.
Move forward to the actual ambush spot, but stop and make sure that you’re equipped with the best gear. You may have picked up some better stuff from the raiders, and every little bit helps.
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The Way It Should Be - The Real Ambush
Engage the group. Try to have at least one person fight the strongest raider. This assassin can do massive amounts of damage and has a ton of health. Tear through the small raiders quickly, while Varric and your mage use some area of effect magic to start wearing away at them. Have Aveline tank them during the battle to try and get the focus of the assassin. You need to keep him from wrecking your fighter, Varric or your mage.
The second group will have 4 stronger raiders and two archers. Have someone engage the archers to pick them off, while a tank also engages the main raider group until you can grind a few of them out. Watch the health of your party carefully, since the assassin can easily kill a weakened member. Use health potions as best as you can. Once you manage to take out the rest of the raiders, it’s basically all free and clear. Kill the assassin to complete the battle.
Confirm the victory with Aveline, then loot the remains of the raiders. Leave through the exit just ahead and go back to the city. You should be able to go right to the Viscount’s Keep from this screen.
The rogue goes down fairly quick, just leaving the leader for an easy kill. Talk to the Guardsman to advance the quest and confirm the Captain Jeven’s role in the ambush.
Leave and advance to the day, and go to the Viscount’s Keep again. Apporach the barracks to get a satisfying conclusion. You can talk to Aveline afterwards to discuss her new position a bit more.
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The Way It Should Be - The Setup
Walk into the barracks and talk to Aveline. She’ll go into the captain’s office, and things won’t go as planned. Well, it looks like we’re not done yet. Time to see who’s dirty in the guards.
Go into Lowtown at night to continue the quest. Be very careful, and avoid the market across from the Hanged Man Inn. There are some huge ambushes with highwaymen, and you may not be ready for them yet. Save often and stick to the back route to get to Guardsman Donnic with only minor resistance.
When you find him in the back corner, there will be four weak thugs and a leader. Just take the thugs out quickly and start on the leader. She’s a rogue, and somewhat tough, but not as bad as the assassin in the raiders. A few more weak archers thugs will pour in from the rear, along with an assassin, so have someone guard the back alley and block them so that Varric can take them out with some well placed shots and spells.
Talk to Donnic once it's over, and you'll confirm what happened and report the captain. You can talk to Aveline back in the barracks to cover her new promotion and her future plans.
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All references and screenshots from "Dragon Age 2".
This information comes from a playthrough on the "Hard" difficulty, unless otherwise noted.