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Retsu Unohana

Bleach manga

Chapter 520, Page 20

Unohana originally was the first captain of the 11th Division and the first Kenpachi.

Masaki Kurosaki

Bleach anime

Episode 8, Masaki's first appearance in the anime.

Bleach manga

Chapter 530, Page 8

This is Masaki's first appearance in the manga.

Chapter 532, Page 16

Masaki reveals that she is a Quincy.

Chapter 532, Page 17

Masaki uses her Spirit Weapon for the first time.

Chapter 537, Page 8 and Page 12.

This is Masaki's last appearance in the manga.

The truth about Masaki's death is revealed.

Royal Guard

Bleach manga

Chapter 516, Page 19

The Royal Guard makes their first appearance in the manga.

The Royal Guard is made up of 5 former Gotei 13 Captains. All the members of the Royal Guard made a significant contribution to Soul Society.

Ikkaku Madarame

Bleach manga

Chapter 205, Page 4 and Chapter 516, Page 9

Ikkaku reveals that he has a Bankai and told Mayuri to keep it a secret.

Shunsui Kyoraku

Bleach manga

Chapter 520, Page 6

Shunsui is appointed as the captain of the 1st Division/Captain Commander of the whole Gotei 13.

Mayuri Kurotsuchi

Bleach manga

Chapter 125, Page 17

Mayuri reveals that he has a Bankai.

Kaname Tosen

Bleach manga

Chapter 146, Page 7

Tosen first reveals his Bankai.

Chapter 178, Page 7

Tosen reveals that he is a traitor to Komamura and Hisagi.

Chapter 384, Page 4 and Chapter 385, Page 18

Tosen reveals to Komamura and Hisagi that Aizen gave him a Hollow form and a Resurrecion.

Gin Ichimaru

Chapter 414, Page 18 and Page 20

Gin reveals the special ability of his Bankai and attempts to kill Aizen.

Zanpakuto

A broken Bankai can never be returned to its former state.

All Shinigami/Soul Reapers receive an Asauchi when they enter The Soul Reaper Academy.

A Zanpakuto can both have a Shikai and a Bankai.

A Shikai is the first release of a Zanpakuto and a Bankai is the second release.

Most captains except for Kenpachi Zaraki can both have a Shikai and a Bankai.

Quincy

All of the Quincy can use a Spirit Weapon.

The Quincy fled the Human World and concealed themselves inside the Shakonmaku after the war 1000 years ago.

All members of the Stern Ritter have a medallion that can steal a Bankai.

The Stern Ritter is a group of Quincy soldiers that have been given orders to destroy the Seireitei.

Most of the Quincy got killed by the Shinigami over 200 years ago in an effort to maintain the balance of souls.