Update. 
Cleaned the EGR and ASV, i was surprised how little crap there was. Put everything back but no difference. I had to grab a couple of filters so stopped in at my local Skoda garage, got talking to the parts guy about the DNF and he suggested one of the spanner monkeys have a look at it. Long story short, they are confident the problem isn't a failing DMF which is great news. 
One thing i have noticed is the Golf has started to intermittently sound more agricultural between 1500-2500RPM, the best way to describe it is like tapping "dry gears" so did a quick scan today and found a couple of faults
2 Faults Found:
009299 - Diesel Particle Filter; Differential Pressure Sensor 
               P2453 - 006 - Implausible Signal - Intermittent
             Freeze Frame:
                    Fault Status: 00000001
                    Fault Priority: 1
                    Fault Frequency: 3
                    Reset counter: 33
                    Mileage: 122297 km
                    Time Indication: 0
                    Date: 2000.00.00
                    Time: 08:40:25
             Freeze Frame:
                    RPM: 0 /min
                    Torque: 136.0 Nm
                    Speed: 0.0 km/h
                    Pressure: 0.0 mbar
                    Text:      -42    mbar        
                    Text:  124    C               
                    Temperature: 15.0∞C
001137 - Exhaust Pressure Sensor 1 (G450) 
               P0471 - 006 - Implausible Signal - Intermittent
             Freeze Frame:
                    Fault Status: 00000001
                    Fault Priority: 1
                    Fault Frequency: 1
                    Reset counter: 40
                    Mileage: 122566 km
                    Time Indication: 0
                    Date: 2000.00.00
                    Time: 14:20:37
             Freeze Frame:
                    RPM: 0 /min
                    Torque: 136.0 Nm
                    Speed: 0.0 km/h
                    Pressure: 63.9 mbar
                    Text:      -42    mbar        
                    Text:  236    C               
                    Temperature: 15.0∞C
No lights on the dash, last serviced 2k miles ago and the oil level is 3/4 up the marker and no performance issues - in fact my MPG is getting better!
Although i cover 90-100 miles a day above most of which is motorway driving at 70mph (ish) i think the first error code is linked to the exhaust pressure sensor error and the DPF should be fine, HOWEVER i might carry out a forced regen just be be sure.
So what could be causing the sound from the engine:
Worn Cam lobs?
Cam lifter?