China, Argentina, Great Britain and Germany have progressed through to the semi-final stage of the Hockey World League Semi-Finals in Valencia, all four teams securing a place at the prestigious Hockey World League Final in Argentina and moving within touching distance of a place at Rio 2016.

The opening match was a humdinger between 7th-ranked China and 14th-ranked Ireland, with the match finishing 1-1 in regulation time, before China clinched the match in the seventh round of shoot-out.

The result means Ireland will now face the 5th-ranked USA, who were felled by some moments of magic from Las Leonas, and Carla Rebecchi in particular.

Great Britain were in a different class to South Africa in the third quarter-final of the day. Two early goals sealed the win for Danny Kerry's team, and from then on they were rarely troubled by a hard-working but largely ineffectual South Africa.

The last quarter-final proved a fitting finale, with hosts Spain coming tantalisingly close to securing a semi-final spot, before Germany proved why they have such a fearsome reputation when it comes to the business end of things.

The semi-final line-up will be China against Argentina while Great Britain face Germany.

Liang Meiyu, was shoot-out hero for China as the Asian side booked their place in the final four after a gruelling encounter with Ireland. China got off to a flying start when Zhang Xiaoxue latched on to a long overhead pass and found a narrow gap at the left post to flick in the first goal after five minutes.

From there, the Asian side sat deep and soaked up pressure before counter-attacking at speed. Ireland did win plenty of corners – eight in the first half – while Katie Mullan was also denied by Li Dongxiao. Ireland's equaliser came from Chloe Watkins, in the second half, with a slap from close range after Kate Dillon’s pass.

This meant the tie went to a shoot-out and the first series of five ended 3-3. The next three were all saved before Liang raced left and slid in the winning shoot-out for a 4-3 success.

Speaking after the game, Liang said: "I was very confident and knew exactly where I would score, we were very well prepared and had been practising since before we travelled to the Netherlands in preparation for this tournament."

Cui Qiuxia explained just what this meant to her team: "This was our last shot at a place at the 2016 Olympics. We knew what we had to do, there was no-where to go."

Darren Smith, coach of Ireland, said: “It’s devastating to lose in a shoot-out. All you want is that ticket to Rio and we will do all we can to try and get that. We put our heart and soul into that match.”

Argentina moved to within touching distance of an Olympic berth as Carla Rebecchi inspired them to a 3-0 victory over USA in the Pan-Am El Classico. Rebecchi fired home a corner rocket before unleashing a stunning backhand shot to build a 2-0 lead at half-time and Noel Barrionuevo whizzed home another from a set piece to kill off the second quarter-final of the Hockey World League Semi-Final in Valencia.

Argentina's Macarena Rodriguez Perez, said: “It was such an intense battle because each side knows each other really well. The goal just after the first quarter was a definitive moment and then we were able to build confidence in the way we play.

“The side is growing up and learning how to build towards Rio in the best form. Because we don’t now have the best player in the world like last year, this tournament is a really good tournament to help us prepare and grow for Rio in 2016.”

Early goals from Alex Danson and Kate Richardson-Walsh saw Great Britain through to the final four in Valencia. "I know we are not there yet, and we still have a job to do, but everything was on this game, we knew we had to win," said Great Britain captain Kate Richardson-Walsh.

Danson and Hannah MacLeod served notice of GB’s intent in the opening minutes, drawing a fine double-save from Sanani Mangisa. And Danson was the one to break the deadlock 12 minutes in as she picked up Emily Maguire’s booming pass. A couple of minutes later, Richardson-Walsh’s swept corner shot took a big deflection off Bernadette Coston – running out number one – to spectacularly bounce off the underside of the bar and in to make it 2-0.

South Africa fought back, winning a couple of penalty corners before half-time with Liné Malan going the closest. The second half saw Great Britain under some pressure but they always had a strong buffer in their favour. 

In the final match, Germany looked to be on their way out of the running, trailing 1-0 to Spain with nine minutes left of normal time. They then trailed 2-0 in the shoot-out before they came back to win it 3-2.

Lola Riera had put Spain ahead when she kept her calm to make it 1-0 from the penalty spot with 18 minutes to go. Germany got level with just under nine minutes through Eileen Hoffmann, forcing the game to the shoot-out. 

The hosts built a 2-0 lead straightaway but Germany clawed back the deficit with Kristina Reynolds providing heroics in goal. Heroine of the hour was Franzisca Hauke who equalised in the fifth round before scoring again in the first round of sudden death. 

Germany's Janne Muller-Wieland said: “We are delighted. It was a big drama and so German of us! Especially after being down 1-0 and then coming back in the shoot-out. It was just amazing and I am so proud of the girls and I want to say we deserved it.

“There are rumours about us that we are never beaten until we are on the bus on the way home. I am quite happy today that this was the case. We fight until the last minute and the last second.”

“GB will definitely be a tough challenge but we definitely want to beat them and not be hanging on and calculating whether we have the Olympic spot or not. We didn’t think about it before now. Tomorrow we will think about it properly but, for now, we are just happy.”