The answer in short is that the file name was incorrect.
Strangely or mistakenly the author of the code, when uploading a given file, added an extra extension so a file would be something like 'image.png' to start off with then when uploaded would become image.png.png. Why didn't I notice this before you may ask? Simply because the whole path wasn't shown in Windows XP (don't ask why I was using XP) when viewing it through the explorer window and I dismissed this issue long before - a big mistake! After trying to find the file by typing the address of the file into the windows explorer address bar and receiving an error that the file doesn't exist, yet I could plainly see it did, a colleague looked at for the file remotely using Windows 7 and we saw that the file was shown as 'image.png.png'. Thereafter the path to the file worked correctly.