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Current captain Ryan Jones joined predecessors Scott Gibbs, Paul Thorburn and Scott Quinnell at a Millennium Stadium launch of the 'Brains SA Captains' Climb' which also has a limited number of places for members of the public who can contribute a minimum of £10,000 to the appeal.
The initiative is the brainchild of national team sports photographer Huw Evans whose family has recently been affected by lung cancer - the disease for which the appeal provides research funding - and he has appointed Ospreys, Wales and Lions No8 Jones as figurehead and chief whip, although rugby commitments will prevent the player from joining the trip himself.
"Each of the fifteen former captains will be competing to raise money for the appeal, so fans can actually sponsor their favourite captain from recent history and it's quite a list of former rugby legends," said Jones.
"Or, even better than that, if you can raise the entrance money you could be reaching the heights of Africa alongside the likes of Gareth Thomas, Jonathan Davies, Scott Gibbs or Paul Thorburn.
"Choose your favourite Wales captain and he is very probably amongst the list of 15 former players who are going and, if that's not enough, how much is it worth to a rugby fan to spend that amount of time in the company of Warren Gatland?"
Money can be donated to each of the individual captain's appeals at the 'justgiving' website by simply visiting www.justgiving.com/brainssacaptainsclimb
Anyone who wants to join the trip or contribute in another way through direct sponsorship should contact the organiser directly at email@example.com
"I recently made the ascent and I can honestly say it was the single most exhilarating, emotional and challenging thing I have ever done," said Gibbs, who was nicknamed 'car crash' as a player because of his seeming ability to run through brick walls and, notably, South African opposition on the Lions tour of 1997.
"When I heard about the good cause I jumped at the chance to join in and get back up there alongside some of my old rugby friends, but I also want to make sure we breach the targets we have set in terms of money to be raised and I imagine all the other former captains will be similarly competitive."
The full list of international captains who have committed to the climb alongside Gibbs, Thorburn and Quinnell is: Gareth Thomas, Ieuan Evans, Mark Taylor, Mike Hall, Bleddyn Bowen, Jonathan Davies, Rob Howley, Rob Jones; Jonathan Humphreys, Bob Norster, Eddie Butler and Colin Charvis. Gatland will also have coaching company with former Scarlets legend and international Phil Davies joining the party.
"This is an opportunity of a lifetime for any rugby fan out there and I'm really looking forward to the experience myself, if not the training that we will all have to put ourselves through to ensure we get to the top!" said Thorburn, who will be one of the more senior members of the party.
"There will be a few dodgy knees and creaking backs amongst us, but I'm pleased to see the likes of Warren, Phil and Bleddyn on the trip who are more from my era. The youngsters may be sprinting up, but I'm backing us 40-somethings to have the extra nous needed to raise the most money!"
The total party will number around 55 including at least one camera crew, Evans himself and the Velindre Cancer Centre's Dr Jason Lester who is leading the expedition alongside 100 Sherpas - and a number of the exclusive public spots have already attracted a great deal of interest.
"The support we have had from the whole rugby community in Wales has been astounding already, the list of names on the trip is truly impressive and if that response is anything to go by we should reach the million pound figure with room to spare!" said Evans, whose wife Sue, a non - smoker, was diagnosed with lung Cancer in November 2008 and is currently in recovery.
"It's only when you are affected by a disease like this personally that you realise it can happen to anyone of us at any time and that we need to do something more about it as a human race.
"The figures just don't stack up in terms of an individual's potential to be affected by this disease and the amount of resources dedicated to finding a cure.
"When we told people about Sue we were overwhelmed by the response and the offers of kindness, people want to do things to help so the next step for us was to channel that energy and begin to raise money.
"Ryan and the current rugby squad were amazing in the Six Nations last year, they all wore pink armbands on the pitch as a show of support to the idea that we could raise a million - that kick-started it and we have gone from strength to strength and I really believe now we are going to do it.
"The list of people who are helping us out is truly outstanding and we can really achieve something with this venture if we can capture the imagination of the fans out there and get them to donate."
Dr Lester, who has treated Evans' wife, is also amazed at the response so far.
"The benefits of what these 15 former rugby captains have agreed to do will reach far beyond the money they raise," he said.
"We are raising the profile of an area of research which gets a bad Press because people wrongly associate lung cancer with smoking, which isn't the case, this disease can and does affect people indiscriminately and we hope to achieve the survival rates that other cancers have already attained.
"It's an area in need of funding and this initiative is an extremely welcome one and one that will do untold good to The Stepping Stones Appeal."
Richard Davies, Sales and Marketing Director at Brains added:
"Like the climb itself, Huw and Sue have set themselves a challenging fundraising target and we're delighted to be able to help them achieve it. With 15 ex captains of Wales climbing one of the highest peaks in the World, we're confident that the 'Brains SA Captains Climb' will be a huge success and generate vital funds for the Stepping Stones appeal."
Secretary of State for Wales Peter Hain is also backing Wales rugby captains past and present as they face one of the greatest challenges of their careers.
Attending the launch at Millennium Stadium in Cardiff today, Peter Hain said: "These are 15 Welsh players who have already reached the peak of their sporting careers by captaining the national team. They now face another daunting challenge as they prepare to climb Africa's highest mountain.
"I'm sure the physicality, athleticism and mental toughness associated with rugby will stand them in good stead for the task ahead. The sense of camaraderie they've all experienced playing for Wales will also help drive them all forward to conquer Kilimanjaro and raise the money for lung cancer research at Velindre Hospital. I wish them all the best of luck with this awesome challenge.
"Fantastic team camaraderie has been seen in abundance throughout this year's Lions tour of South Africa and I'm sure all the captains would join me in wishing the current Lions squad all the best as they prepare to restore the Lions' Pride in the third Test on Saturday."