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I have carried out several tests comparing Velvia 100 with Velvia 50 and a couple comparing it with Provia 100F. Unfortunately Velvia 100 has a very troubling tendency: when presented with colours at the red end it can, at times, grab them and exaggerate them too far (without the use of any filters). For example I photographed a very striking honey coloured rock with some red and green seaweed in the background. This was in overcast but bright conditions (EV14) using Velvia 50 and Velvia 100 as well as two different lenses (Schneider XL 110mm and Fujinon T 300mm). With each lens the two exposures were made within one minute of each other and there was no change in the conditions. As expected the Velvia 100 versions are not quite so saturated as the Velvia 50 but perfectly good in this respect all the same. However the Velvia 100 versions are far too red and seem to me to go beyond what is acceptable. This is the case for both lenses, thus the problem is not due to some characteristic of either lens (neither of which has ever given me cause for concern on this or any other account). This exaggerated red rendition applies to the main rock and many pebbles as well as the red seaweed; the green seaweed is acceptable but lacks the richness of the Velvia 50 rendition. This is not a matter of colour accuracy (since landscape photography is an art rather than scientific documentary) but the rendition of colour should look convincing and be inviting rather than questionable. Naturally these are matters of taste but there are limits; clearly mine have been exceeded in this case. Here are the two photographs made using the Schneider XL 110mm lens:

Rock Velvia 50

Velvia 50

Rock Velvia 100

Velvia 100

Of course your monitor might not show the exact colours (depending on how it is calibrated) but the difference should still be clear, in particular the Velvia 100 image will appear singificantly redder than the Velvia 50 one. Unfortunately the subtle differences, e.g., the shade of the green seaweed, are lost in the low resolution scan for the web. I have observed this behaviour with other photographs; the two reproduced here are enough to illustrate the point.
These observations have been confirmed by fellow photographers one of whom found that when used with open landscapes the new film can produce an unnatural red cast in skies. I have tried this at sunset and found the same problem. The following photographs were made within a few minutes of each other.

Sunset Velvia 50

Velvia 50

Sunset Velvia 100

Velvia 100

In two other photographs where there was no red in the sky I did not find a problem. For one comparison conditions were overcast (actually it was raining) and in this, the clouds as well as the overall sky are fine (but again the foreground coastal rock is more reddish than the Velvia 50 version made for comparison though in this case it is not unacceptably so). The same is also the case in another photograph made in fairly bright conditions but about three hours before sunset. All these photographs were made on the same location on the East Lothian coast in Scotland.
This strange and somewhat erratic behaviour with the red end is the one major problem I have with the new film (the increased speed is a minor inconvenience since I like long exposures; carrying yet more filters is not my idea of fun). Used in many conditions it is fine, e.g., I have used it in cloud/mist on Schiehallion and it has produced a very beautiful rendition with a light blue cast (as I wanted). On the same day I made a study of some pink rocks and that looks natural and very attractive (as distinct from accurate). I have also used it with a long exposure time (15") and found no problem.
Compared to Provia 100F, Velvia 100 is more saturated as expected. I have made two comparisons: one of wild garlic under tree cover with a carpet of brown leaves in the foreground. The greens are deeper with Velvia 100 as are the browns (in fact Provia 100F gave the more neutral result as would be expected but the Velvia 100 version is the more attractive one this time). The other comparison was of a common spotted orchid (white variation); similar comments apply here. This is not to say that Provia 100F can be discarded for landscape photography, it is wonderful for many subjects (for which Velvia 50 is unsuited) and I always have some in my rucksack.
My conclusion is that Velvia 100 is far from being a replacement for Velvia 50; it is a very different film. If it was an addition to the range there would be no problem. As matters stand I can only hope the Fuji will resolve the odd behaviour with the red end of the spectrum, or better still produce a genuine equivalent of Velvia 50 (I don't mind if it carries with it all the known foibles of this amazing film, the good points make them more than a price worth paying).
Good News: Fuji announced in a press release dated 7 November 2006 that the re-launch Velvia 50 into the UK market. They used substitute raw materials in place of the ones whose unavailability caused the stop in production of the classic Velvia 50. The aim was to mirror the characteristics of the classic emulsion. Re-introduction was planned for spring of 2007. I have since used the replacement film on a few occasions and find it excellent, it is not identical to classic Velvia 50 but that is not a problem. The only reason I have not used it more is because I still (as of 2016) have a stock of classic Velvia 50 in my freezer.