The officers will be given special training before being deployed
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The Foreign Office has launched a campaign to recruit up to 200 police officers to serve in Iraq.
The volunteers, who will form a pool for duty in the region, will help maintain security and train the local police force.
Up to 100 are to be deployed at any one time with the rest on standby, according to the Foreign Office.
Officials said the group would be armed and given special training, but would not include officers currently authorised to carry firearms "due to domestic policing requirements".
A date for the first deployments has yet to be decided, and will depend on how the situation in Iraq develops.
Foreign Office Minister Baroness Symons said security was a key issue for Iraqis and removing Saddam Hussein had already made them feel safer.
Mentoring duties
She said: "The police volunteers who go to Iraq will have the thanks of this government and of all the people of Iraq for the key task they will perform."
Home Office Minister Caroline Flint said: "The professionalism and expertise of our officers will be invaluable in reforming the Iraqi Police Service.
"Officers will be deployed only when conditions are right and every effort will be made to ensure their safety while on the mission."
The group will conduct mentoring duties and those with the appropriate skills could be deployed elsewhere to assist with the out-of-country training of the Iraqi force.
The move follows the departure last month of two senior police officers for duty in the region.
Deputy Chief Constable Douglas Brand, of South Yorkshire Police, travelled to Iraq to act as senior mentor to the Chief of Baghdad Police.
And Deputy Chief Constable Stephen White, of the Police Service of Northern Ireland, is stationed in Basra as a senior police adviser.