Might this be how the Turin Shroud was faked, using medieval alchemy?

Here it is folks: the best I can offer after more than 3 years  of almost non-stop experimentation : Model 9  ("the nitric acid model").

Alternative name (afterthought, added 25th April): this new technique produces what might be called a "tactile chemograph".  Maybe there was only one ever produced (the image that we now call the Turin Shroud).  The tactile chemograph may be thought of as a forerunner of the photograph. (In both instances, one produces a latent image from a real person without harming them in any way, one that can then be developed in a bath (or vapour chamber) with the appropriate developing chemicals.

That's my own (right) hand.  Behind it is a negative image on linen of my (left) hand produced using the new (?) technology. I've had to mix left and right to make a comparison (imprinting not only produces a negative image but  left-right reversal too)

Here's the same negative image in close-up. I've cut out the unsightly part where there was excessive manual  moulding of linen to side relief (but was able to utilize the removed portion for fruitful experimentation).  As mentioned in the preceding posting,  the cut out was used to test the effect of neutralizing the excess nitric acid, with the unexpected effect of enhancing both image colour  (yellow to yellow-brown) and the contrast CHEMICALLY - not digitally.

Details will follow. That's if anyone is interested (comments invited- see sidebar for quick link).  If not I'll leave it at this - short and (arguably) sweet and take a holiday from scientific model-building for a while (weeks rather than days).  It can be an exhausting business, and somewhat hazardous too when fumes off concentrated nitric acid are my suggested means for  producing the elusive result - that 'enigmatic'  and highly superficial Shroud of Turin image - at least at the macro level.

Reminder (from posting preceding this one):


Step 1:Imprint off 3D template (possibly a real person, living or dead OR an effigy thereof in wood, stone, clay etc) painted with heat-gelatinized white flour.

Step 2. Develop the proto-image by exposing to nitric acid (HNO3) fumes

Step3. Neutralise the unreacted acid in the fibres (e.g. by dusting with chalk, or rinsing with lime water).
 

Here's an earlier picture showing the crucial testing of the third step (neutralization of acid) performed on the unsightly excised portion of the hand imprint.

The portion on the right is the untreated control, i.e. hand imprint after partial dissipation of nitric acid fumes in air (outdoors!).

The left hand portion was cut off between the two crosses. That.s when I noticed the stiff nature of the image area with a coarse texture (hardly surprising, given that flour is mainly starch). Would the stiffness disappear if the cloth were washed, while leaving the image? But first, there was another test that could be done before wetting the fabric. I crumpled and kneaded the fabric. Immediately the fabric in the image area began to disintegrate, assisted no doubt by the presence of the stiffening agent that assisted thread fracture. All the more reason, then, to minimise the weakening of the linen by getting the fabric from the fumigation chamber into a weak alkali solution ASAP. The left hand portion in the photo above was the appearance AFTER doing just that - immersing the offcut in sodium bicarbonate solution, testing before and after with pH indicator to check that acid had been neutralised, then rinsing thoroughly and drying.  Not only had the image not washed out, but it had intensified and changed from yellow to yellow-brown, becoming arguably more Shroud-like.

Expect some more experimental details to be added in the next day or two, plus the results of imprinting off a miniature effigy made from moulded clay (after air-drying and sealing).

That's the home-made template on the right, alongside the brass crucifix used in so many of my previous "heat scorch" experiments. Quick-drying emulsion paint was used as a sealant (what would medieval folk have used to seal the pores of unfired earthenware on wonders?). Imprints are developing in acid fumes (locked garage) as we speak.

Some details re the imprinting technology thus far (as promised)

I used my right hand to paint the left one with a thick paste made the previous day using white flour and hot water (it set to a gel overnight in the fridge, which reverted to a paste on stirring). Linen was placed on top, as shown, and then pressed down firmly to produce an imprint on the underside of the linen. Note the considerable detail in the imprint, even at this early stage.

Here's an early stage in setting up the fumigation (garage! eye protection?  face mask! ).

The linen with its flour imprint has been stuffed into the 'goldfish bowl', secured with the blue tape to leave a clearance between fabric and base to leave room for acid. The concentrated nitric acid (hazardous! not for the faint-hearted) is then introduced via the funnel so as to form a 1cm deep layer under the fabric without touching it directly. The idea is to funigate the image. After carefully removing the funnel a sheet of glass was used as a lid, weighed down to get a reasonable seal. The garage was then vacated ASAP and locked with a no-entry sign on door. Chemical development took place overnight.

Here's the imprint after development with nitric acid, but before neutralizing the excess acid. There's not a lot to see at this stage, and it's still a chemical hazard, needless to say.

Here's the developed imprint in the wash hand basin, ready for rinsing and neutralization of unreacted acid with sodium bicarbonate.

Ready to neutralize the excess acid.

The acid has been neutralized (the pH now being greater than 7). Already the image on the linen looks darker (now more brown than yellow).

Final step: after thorough rinsing and drying, the imprint can be safely ironed, ready for displaying on one's blog... 

Note: there are no reasons for thinking this image is not a permanent one, but time will tell.

All the photos on this posting are 'as is' from the camera. Apart from cropping, there have been no changes to brightness, contrast or other photoediting.


Afterthought: who'll be first to say that I've failed to produce a perfect facsimile copy of the fingers on the Shroud - that mine are ordinary everyday sort of fingers, not the spindly unnaturally elongated fingers one sees on the Shroud?  As for the hint of fingernails on my image - well, that rules it out of contention straightaway! You read it here first.

Afterthought to afterthought: there's a simple answer to those overlong fingers on the Shroud. The subject was alive, say a non-deceased medieval monk, and his hands shifted during the imprinting process. Maybe the imprinter briefly applied to much pressure, causing the hands to slide on the slippery abdomen, creating a skid-mark effect, captured for posterity.

Update:  Wednesday 22 April, 15:10

I have a new imprinting medium, a very different one from the flour gel used so far. It's of animal origin, not plant, it requires much shorter development times, and if I'm not mistaken, appears to protect the background non-image areas of linen (maybe 'trapping ' nitric acid more efficiently?). What's more it was well known in medieval times, indeed for millennia.

Here's what an imprint off my trusty brass crucifix looks like with the new wonder material after neutralizing excess acid, and applying the autocorrect menu option to the snapshot:

 Here's a light/dark reversal, using the Edit Invert function of ImageJ (autocorrected for additional contrast).

Update: Wednesday April 22, 22:00

Here's a further responses or rather query, regarding  the new model, appearing just now on shroudstory.com, and my immediate reply.

Thibault HEIMBURGER

April 22, 2015 at 3:04 pm

Reply

 

Colin,
Can you explain in detail the advantages of your new hypothesis with regard to your ‘old’ scorch hypothesis

Colin Berry

April 22, 2015 at 3:47 pm 

Off the top of my head (maybe with afterthoughts later):
1. One can imprint off a real person (or statue, bas relief etc). The imprinting medium (flour paste etc) is non-injurious to skin.
2. One can mould the linen to contours manually if desired, capturing as much or as little of the 3D relief as one wishes (with more or less risk of lateral distortion).
3. Development of the image in the fumigation chamber can be monitored visually at intervals over minutes or hours until one has obtained optimum image intensity, and the least damage to linen fibres.
4. Retained acid fumes after development can be neutralized, either with lime water, or by dry dusting with powdered chalk. However, some weakening of fibres must be expected.
5.The end-product can be claimed to be an ancient sweat imprint, left on Joseph of Arimathea’s linen when the body was transferred from cross to a makeshift stretcher/body bag.
6. The technique allows for blood (or blood substitute) to be applied at the same time as body-imprinting medium, provided the blood or substitute stays red in nitric acid fumes (real blood does not – it quickly turns a brown colour). Blood would have been applied after. i.e. directly on top of the gooey imprinting medium to account for there being no body image under Shroud “blood”.
7.The use of an extraneous organic material (flour etc) allows for the possibility of the newly-imprinted and developed image being conspicuous, but slowly fading over the centuries as the pigmented material flaked off or became otherwise degraded, provided there was a fairly stable “ghost image” left behind, the one we see today.
8. When applied to new linen, the technique has a side-effect that would be seen as a bonus – artificial ageing of the linen. Centuries later, pro-authenticity chemists and others would be delighted to find there was less potential vanillin and more mechanical weakness than would be expected of medieval linen a mere 700 years old.
9. An imprint developed by oxidation and/or other chemical reactions may (or may not) lack the fluorescence of a thermal scorch image.
10. Chemical action of limited duration may result in more superficial change to linen fibres than is possible by thermal scorching, such that one sees no colouring at the interface of the SCW and central lumen. Reverse-side coloration can be minimized by suitable adaption of technique (thick linen, use of sizes to block up pores, use of viscous imprinting media etc).
As properly noted, all this is simply an hypothesis at this stage, one that will need a lot of experimental work to evaluate, with the possibility of premature paradigm death at any stage. However, I shall be taking a break from experimental work for at least a fortnight probably longer, these last few weeks having been fairly hectic, spent in and out of the garage, trying to avoid or escape acid spillage and acid fumes, first with the H2SO4, and now with HNO3 (Phase 1 complete).

Update Thursday

...and the last of those comments had this appended as a postscript, though how many get to see it when a single individual then posts 6 comments in short order (more on the way?) remains to be seen. This blogger NEVER forgets those who abuse blog sites that have a fixed number of entries under Recent Comments, in this instance 10 only.

Colin Berry

April 23, 2015 at 4:10 am

PS. After sleeping on that list of 10 points, all I would add for now is a gift wrapper in dubious good taste (thinking of the sensibilities that prevail generally on this site, with one or two notable exceptions).
There’s a bit of code in scientific research, summed up as “looking where the light is”. Charles Freeman is the historian with his “just a painting” thesis (dogma?) who is simply “looking where the light is”. PDL and his under-occupied ENEA pals with their employers’ laser beams are also looking where the light is, or what they imagine may have existed for a one-off instant in time, (and thus beyond the remit of science, JoeM).
My latest hypothesis explains why the TS is also a one-off, but of medieval provenance,and while difficult to fathom, is still definitely within the remit of science, provided one is prepared to think like a medieval, and not confine one’s search to where the light is.
My new starting point, a year or so ago, was to regard the TS as an attempt to replicate Joseph of Arimathea’s linen as it might have looked on arrival at the tomb, BEFORE being replaced by the real burial attire, i.e. Nicodemus’s “winding” sheets after washing and spices, oils etc. It was intended to be a bigger and better whole-body, front and back negative imprint (NOT painting) that would trump the Veil of Veronica, then the major draw for medieval pilgrims according to Neil McGregor, recently retired Director of the British Museum.
The task was to simulate a conjoint sweat and blood imprint, but to do it in a way that could/would stand up to the closest critical and sceptical scrutiny (barring the canny bishops of Troyes, watching the upstart ‘relic’ drawing funds away from their own cathedral upkeep ).
No, they did not scorch the body image with a heated template, not if the aim was to simulate an ancient sweat imprint. They consulted an alchemist, possibly one with a sympathetic religious disposition (Paul of Taranto, the Franciscan monk?). He in turn delivered state-of-the-art proto-chemical technology, in the form of nitric acid fumes, guaranteed to turn virtually any organic material into a yellow or brown stain on linen. Sure, it weakens the linen itself, but then the fibres on the TS ARE weaker than expected for something that is only 700 years old according to the radiocarbon dating (objections noted).
If as I suspect Paul of Taranto, or someone similar, was the brains behind the TS, then we have an explanation for why the TS image is exotic and such a well-kept secret (our alchemist/cleric may have thought that in harnessing his (al)chemical know how for the greater glory of God, he was saving souls that would otherwise have endured everlasting torment. In short, the ends justified the means. A similar hard-headed philosophy appears to prevail to this day (viz. current exposition in Turin).

Update: Friday 24th April:

David Goulet has asked how that hand imprint above responds in ImageJ.

Here's the result - a 5 minute job with no attempt to find the 'perfect' combination of settings.

Here's a Secondo Pia type light/dark reversal, one that restores the 'negative' image to a positive. (Used Edit Invert in ImageJ).

And here's the effect of some minor changes to the default settings in ImageJ's 3D rendering option. I've seen better. I've seen worse .

The Turin Shroud. was this the world's first and only tactile chemograph (think of it as a primitive 'photographic' negative, except for one tiny detail. Neither light not any other kind of electromagnetic radiation played any part in its production. It relied on the human touch (well, gentle massage actually).

What finally persuaded this blogger to abandon thermal scorching, and move to liquid (or semi-liquid) imprinting? It was that paper that Joe Accetta PhD presented at the St.Louis gathering, 2014, in which he propsoed that the TS image had been produced by woodblock imprinting. Up till that time I'd always been sceptical re the use of any kind of liquid imprinting medium, considering that would risk a reverse-side image. But I concocted my own equivalent of Joe's "oak gall" imprinting ink, in which the iron salts probably have a mordant action, as well as creating the ink by reaction with plant tannins. Here's an image produced, substituting tannin-rich pomegranate rind extract for oak galls, supplemented with iron (II)sulphate.

That 'wet' image was as good, if not better than anything produced by scorching. Yes. there was some reverse-side penetration, but might that not be minimized by suitable modification of technique, or simply by using thicker linen (and the TS linen IS thick, as Hugh Farey has observed).

Once liquid imprinting was permitted as an option, then a host of new experimental options were opened up. Thanks Joe Accetta. You weaned me of those thermal scorches (but they were useful in other ways, showing that ANY negative imprint can model certain key features of the TS, notably negative image and 3D-enhancibility). Models in science do not need to tick all boxes simultaneously. One can run different models in parallel, each earning its keep in one or other respect, while patiently waiting for the day when the super-model suggests itself, one  that combines the best features of its precursors, not only mine, but those of Garlaschelli and Accetta in particular. Hugh Farey and Adrie van der Hoeven added some useful and thought-provoking grist to the mill too, though whether they and the previous two would approve of the end-result is another matter.

Might tactile chemography prove to be the super-model? We shall see. These are early days, but I'm (how shall we say?) quietly confident.

Update Tuesday 28 April

Where next? Here are some thoughts posted earlier today to shroudstory.com:

1. 

   Colin Berry
   April 28, 2015 at 12:49 am

   Reply

   As indicated earlier, I’m taking a break from experimentation, while taking stock of results so far (and the trickle of comments here and elsewhere).
   There are some new variants I shall be testing re the initial imprinting and subsequent development.
   Imprinting: is it better to do it as already described, with the imprinting medium placed first on the subject, before draping the linen over, OR is it better to do it Garlaschelli style (“frottage” as he calls it) where the linen is placed over first, and the medium then added last for moulding around contours?
   If I stick with my procedure, is it better to imprint LOTTO or LUWU configuration, those acronyms having been tested in my contact scorch model. (LOTTO = Linen On Top, Then Overlay; LUWU = Linen Underneath With Underlay) Each has its pros and cons where an inanimate template (statue, bas relief etc) is concerned, while for a real human being LOTTO is better obviously then LUWU.
   Then there’s the imprinting medium. The pilot study used a hot water dispersion of white wheat flour. I’m thinking of trying a cold water dispersion, so as to have intact endosperm cells.The latter have their starch granules and storage protein nicely enveloped in a primary cell wall sac whose composition will probably not be dissimilar from that of the superficial PCW of the linen fibre.
   
   
   

   

   Cross section of wheat grain. Note the internal cellular architecture of the endosperm, and the 'graininess' of the latter due to starch granules and storage protein.

   
   
   
   
   

   

   SEM photomicrograph of internal structure of the wheat grain, Note the large endosperm cell, note its thin (primary) cell wall, note the much smaller starch granules within the endosperm cells.

   
   On the general principle that like is attracted to like in organic chemistry (polar/polar; apolar/apolar) , there might be something to be said for bonding a compatible microparticulate substance to the linen first as a possibly more receptive carpet for image capture.
   Finally, I shall try substituting a purely thermal treatment for nitric acid vapour.(essentially Garlaschelli technology). That too might produce a TS like coloration and image, either by oxidation of carbohydrates OR via Maillard reactions between sugars and proteins (yup, we’ve been there before in the scorch model, but here the chemistry is being tested in the new two step imprinting/developing model for which I have high hopes.
   
   Update Sunday May 3
   
   This comment has just appeared on the shroudstory site.(I've omitted allexcept the last paragraph):
   
   

   

   daveb of wellington nz

   May 2, 2015 at 7:34 pm

   Reply

   
   Colin has now been attempting to reproduce the properties of the image for some three years, with indifferent success only, although I applaud his perseverance. Might we suppose that a less chemistry-informed artisan would have struck it lucky any sooner? As one early commentator observed, Colin is more likely to end up proving the resurrection from all his efforts.
   
   Don't you just love the man's pomposity?
   
   Here's my reply (Yes, I'm sitting on something just 12 hours old that could give the new model a real boost):
   
   

   

   Colin Berry

   May 3, 2015 at 12:22 am

   Reply

   Colin is continuing to do open-ended experimentation. He has just stumbled on an entirely unpredicted effect with his new cheiropoietic hand/flour/water model (Stage 1 imprinting), one that is arguably replete with possible implications re image fuzziness. It’s to do with instant adhesion, dare one suggest ‘medieval superglue’. It’s to do with instant fleecing-up of linen. Details later.

   
   .
   
   Ooops. I'm doing myself down in that comment, since I did in fact predict the effect just a week ago in these words from above:
   
   "On the general principle that like is attracted to like in organic chemistry (polar/polar; apolar/apolar) , there might be something to be said for bonding a compatible microparticulate substance to the linen first as a possibly more receptive carpet for image capture."
   
   Have been on holiday this last week. Mind's gone a blank.
   
   The key word? The new lead?  Answer: adhesion. That's instant adhesion.

The enigmatic Shroud of Turin: experimental testing of my novel nitric acid fumigation model is currently underway (preliminary results look distinctly PROMISING).

The posting immediately before this one describes my preliminary findings with the new model which are most promising: an imprint onto linen from a 3D template, made using a paste or gel of white flour turns a Shroud-like yellow-brown in colour when exposed overnight to nitric acid fumes. What's more, the non-image areas of the linen acquire a beige coloration that might well be described as artificially "aged" in appearance.

I have experiments going right now to see if I can't improve on the somewhat blurred and indistinct image obtained so far off my brass crucifix. If I had access to a larger fumigation chamber that safely contained fumes within my garage, I'd be attempting to image off myself (IMPRINT only!) starting with a hand say (though a finger or two might be possible within the stoppered bottles (jars?) being used at present.

Here a picture taken an hour or so ago of the current experiments out in the sunshine, on the patio table.

They are now safely back in the garage and the test linen strips will be removed and photographed tomorrow (results on this posting). I'm not sure if the brown fumes of NO2 are evidence of the nitric acid quickly finding components to oxidize (hemicelluloses?) or merely photodissociation of HNO3 in the sunshine. I'll need to set up extra jars to test this and other 'good housekeeping' hypotheses. One is still on a steep learning curve with the new system.

 While twiddling my thumbs, waiting for the images to develop in those jars (yes, let's call them jars, being fairly wide-mouthed) I've been thinking some more about the mechanics of fumigation, performed medieval-style. Some might consider it a tall order (or wide order?) to fumigate a 4.4 x 1.1 metres length of linen. I'd previously suggested it was done 'landscape' rather than 'portrait' orientation, if only to suggest a raison d'etre for the peculiar side strip removal and re-attachment (see previous posting).

Well, I've been having second thoughts, as you will now see from some simple modelling with folding to get a compact package for fumigation.

That's an image of the TS you see above, printed out onto A4 paper, with the edges guillotined. The ends corresponding with frontal feet (left) and dorsal feet (right) have been labelled.

Here's the same after folding lengthwise and then width-wise. This would now represent a more convenient package for fumigation if suspended at the gathered feet end (top) , ie. 2m x 0.5 metres approx.

Here's the same, suspended by a thread. Note that the imprinted surfaces are all freely exposed to the fumigant. So too, though more cramped by converging surfaces, is the reverse non-image side, except possibly for the crease area between frontal and dorsal head.

Given that our medieval  forbears built magnificent cathedrals that still stand to this day, it seems reasonable to suppose that a suitable chamber could be found for exposing the above package to nitric acid fumes. The latter was produced from high-temperature calcining of a mixture of  Cyprus vitriol (copper sulphate)/alum (potassium aluminium sulphate) / saltpetre (potassium nitrate). That's the reaction mixture prescribed by the 13th century alchemist Pseudo-Geber, possibly one and the same as the Franciscan monk, Paul of Taranto (see my previous posting). The nitric acid (HNO3) fumes from the retort could have been  used directly, or could have been condensed into a cooled receiving flask, and then reheated to produce the same HNO3 at leisure (obviously more convenient to do in separate steps).

A suitable chamber for fumigation? Given the compact dimensions from my folding experiment, maybe a small brick built kiln of some kind, or reinforced clay-built enclosure, taller than it is wide. Maybe the side strip can be re-accommodated within this 'tall' configuration, maybe not.

See also my comments placed on a shroudstory.com posting for more details of my thinking re the potentiality of this current 'fumigation' model.  There's much to be done, many TS characteristics to be matched (image superficiality, non-fluorescence etc) but I'm quietly becoming more confident by the day, by the hour that this might finally be the answer that has eluded us bumbling science bods for so long...

Update: Monday 13:45:

Somewhere I've read that the head image on the TS is 10% (?) more intense than the rest of  body.  (will try to track down a reference).

Yup. Located. 2005 Dallas meeting.

"The luminance level of the head image in the positive photograph of Durante (2000) is 10% and more lower (darker) than that of the whole body image(Moran 2002)"

Conversely, we all know that the feet at the opposite end on both frontal and dorsal halves are scarcely imaged at all.

The proposed geometry for fumigation shown above offers an immediate explanation.  The head is close to the source of acid-fumes, fed in from the lower end, while the feet are furthest removed. In other words, the difference in image intensity is maybe not the result of an imbalance at the imprinting stage (difficult to explain) but an imbalance at the stage of image development.


Update Tuesday 21 April


While waiting for my latest imprinted linen samples to develop in their fumigation chamber, I've been taking a glance at Dan Porter's shroudstory site. The current posting has a thumbnail picture of an unused portion of the Arizona sample for radiocarbon testing.

It's credited to  "STERA" 2012 , and sure enough one can find Barrie Schwortz's account on his internet site of how he was invited back to the Arizona lab to take that and other close-up pictures.


Looking at it, one would hardly credit it was linen, even 2000 year old linen, not that I'm an expert where the latter is concerned or even medieval linen. But if anyone had shown me that sample 'blind' and asked me to identify its origin, I'd have said it was jute sacking.

But now I have an advantage over others. I have seen what nitric acid fumes do to linen, turning them a beige-colour, though admittedly not quite the honey-coloured appearance you see above. I've also seen what happens when one places nitrated linen on a hot ring - it chars much faster and more extensively than control untreated linen. Here's that same snapshot again:

 Are we seeing the 'real' reasons why the present Shroud in Turin is extensively damaged by "hot pokers" and fierce fires in cathedrals?  Might it have been less damaged by either of those if it had been plain untreated linen, not nitrated linen as I now propose?


 Might the honey-coloured TS linen be the colour it is on account of the "relic" having been produced by my novel two step-process - imprinting off a 3D subject with flour paste, followed by chemical development with nitric acid fumes?

Looking at that STERA image above has just reminded me of two further pieces of evidence that fit with the new hypothesis:

1. The absence of vanillin (or, as this blogger prefers to call it, potential vanillin) in the TS, cited by STURP's Ray Rogers as evidence of the TS being much older than the medieval dating.

2. The more recent work by Fanti and his colleagues on shed fibres retained between TS and its backing Holland cloth that were aspirated/harvested at the time of the 2002 'restoration'. Those fibres they claim have mechanical and spectral properties that make them closer to 2000 than 700 years old.

All is explained in the new model. Nitric acid fumes, being powerfully oxidizing (among other things) do in a few hours what would require centuries to achieve by slow atmospheric oxidation. The fumigation did not just convert an imprinted flour image into a  pseudo-sweat imprint left on Joseph of Arimathea's expensive linen. It gave the entire bolt of fabric an aged appearance, like that which one sees in the Schwortz photograph above. Indeed, it may have been knowledge of what the 'new-fangled' nitric acid of the 13th/14th century did to linen and other fabrics, and then to skin and other organic materials that planted the idea in someone's head that nitric acid could be used to create a sensational new entry for the  booming market in "newly-discovered" holy relics.


Speaking of Ray Rogers (may he rest in peace) here's something this blogger wrote back in June 2012 regarding his diffusion/Maillard model (that lives on in numerous sindonological sites to this day, despite having scarcely a shred of scientific evidence in its favour). Note my words in red:

"There is other evidence too that the assumption by Rogers that the image is in an impurity layer (largely based it seems on the writings of Pliny), formed by a Maillard reaction between supposed reducing sugars in the impurities and volatile amines from post mortem decay (cadaverine, putrescine etc) is ruled out by Rogers’ own observation in the same paper that the Shroud’s image-bearing  areas are not enriched in nitrogen. (All amines contain nitrogen, the amine group being -NH2)"

Have I now been hoist by my own petard? The model proposed here also requires there to be extra nitrogen, indeed extraneous nitrogen in Shroud image areas, as does/did Rogers' credulity-stretching model.

I'll be back later today to address this problem. Those impatient to know the (possible) explanation for a nitrogen anomaly can get some of it in the conversation I had with  Adrie van der Hoeven on the posting preceding this one (see Comments).

If you search for (nitrogen analysis methods) as I have just done, all 10 returns on the first page refer directly or indirectly to the Kjeldahl method. But while that measures most nitrogen in human, animal and plant tissues (proteins, peptides, amine and amide nitrogen) it does NOT measure nitrates, whether as nitro substituents (N bonded directly to C as in "true" nitro-derivatives, i.e.  -C-NO2) or as nitrate esters, e.g. -C-O-NO2, with an oxygen bridge between C and N. But was the TS nitrogen measured by this time-honoured method? The Kjeldahl procedure is traditional wet chemistry, usually done for materials where there is no limitation on sample size. OK, there's a micro-Kjeldahl variant, but I for one can't say as I ever recall having seen the K word linked to the Shroud. So how did Rogers and others determine the nitrogen?  X-ray fluorescence? One hopes that the absence of a peak on that kind of scan was not taken to mean nitrogen was missing (as elsewhere we see a STURP claim for the absence of aluminium). X-ray fluorescence is generally reckoned to allow detection of elements above chlorine (atomic number 17). Nitrogen is element number 7 (far too small). Aluminium is element number 13, still too small. Was a third method used by STURP to determine N? I doubt it, but stand to be corrected.

Update Tuesday 13:20

Here's the very first attempt to imprint of my own hand, using the new two-step flour gel/nitric acid technology.  I used the back (top surface) of the left hand to be precise, and the right one to apply pressure to the overlying linen, with gel-painted hand underneath.

 As I say, these are early days. There is much optimization needing to be done, but the method works in principle. The circled area is probably due to excessive wrap-around, i.e. moulding the linen to the vertical side of the hand. In future it must be vertically downward pressure, so as to restrict the imaging to the highest relief, and producing a quasi-bas relief, despite the fully 3D nature of the 'template'.

Taking stock: flour was chosen as initial prime-focus imprinting medium for historical and chemical reasons. First, it's been a component of the human diet, cooked especially, not just for centuries but millennia. Second, while mainly starch, there's a reasonable proportion of protein too (approx.10%) so one covers one's bets where the developing agent is concerned. Nitric acid will tend to dehydrate /oxidize carbohydrates, whether starch or non-starch polysaccharides, to  brown caramelised products, with the added possibility of yellow nitration products too (see previous postings for the propensity of conc.nitric acid to give the so-called xanthoproteic reaction with aromatic side chains of proteins which are bright yellow.

The flour works in principle, but it's slow, and the final images are not quite as distinct as one might wish against the off-white background.

So what are the alternatives? Egg white has been tested, and gives a prominent yellow imprint, as expected, albeit requiring overnight development. But there is reverse-side colour as well, which one hardly sees with the gelatinized flour pastes. So it's thinking cap on : what else might have been tried on a trial-and-error  basis? Might one need to test mixtures, say of wheat flour and additional protein, the latter in a form with little tendency to migrate through the weave of the cloth.

Update: 17:00 Tuesday 21 April 2015

Oops. I (nearly) gave up too soon on that hand imprint, the one reported above that initially looked so unpromising. Well, it's been further processed (Step 3) and  the result is methinks deserving of a new posting all to itself. What did I do that made the difference between (possible) success and abject failure? Answer - I washed out and neutralized the excess of nitric acid remaining in the fabric after fumigation (as our proposed medieval alchemically-literate relic-forgers might have done).

Yes, there will be a new posting, this very evening, once that 3-step imprinted linen is fully dry and re-photographed.

Reminder:

Step 1: imprint off 3D template (possibly a real person, living or dead OR an effigy thereof in wood, stone, clay etc) painted with heat-gelatinized white flour.

Step 2. Develop the proto-imageby exposing to nitric acid (HNO3) fumes

Step3. Neutralise the unreacted acid in the fibres (e.g. by dusting with chalk, or rinsing with lime water).

Modelling the Turin Shroud (medieval fake?). Just waiting now for the nitric acid to arrive.

Yes, an email arrived yesterday to say that conc.nitric acid has been despatched, and might arrive as early as today (10th April) or anytime in the next 10 days (grrrr).

I'm all ready and rarin' to go with my dastardly new approach to modelling the Shroud, one that depends on imprinting a  negative image onto linen from a template (or person?) coated in organic matter (to simulate bodily sweat), not forgetting those blood stains either in all the biblically-correct places. Then follows the crucial step: exposure to a mix of nitric acid and NOx fumes (see posting that preceded this one for the chemical whys and wherefores).

Here's my miniaturized set up for doing the experiment in the garage, with a crude but hopefully effective system of containing the fumes.

Set up for fumigating imprinted linen with vapour phase HNO3/NOx fumes

The conc. nitric acid will placed in the broad-necked bottle - a cm so of depth should do. I may or may not add a few copper turnings to augment the supply of NOx (some forms naturally as a result of HNO3 photodissociation). The imprinted linen will then be suspended in the air space, using the ground glass stopper to hold it in place. Imprinting procedure? I'll paint that brass crucifix with some stiff protein gel for starters (that's powdered gelatin in the green/red sachet), and press down onto the linen to get the negative "body" imprint. (Note that a real body could be used in any scaled-up version, similar to Luigi Garlaschelli's memorable modelling via 'powder frottage' (though he too tested a slurry).

The sealed reaction vessel will then be placed in a gripseal poly bag, at the bottom of which will be some slaked lime or sodium bicarbonate (shown) to sequester any escaped acid fumes. Naturally I'll be wearing a makeshift face mask and goggles, though I survived decades in  chemical, biochemical and medical laboratories without them (but they had fume- and spill containment facilities that my home garage lacks). Wish me luck, all those of you who share my curiosity as to how the Shroud was REALLY made (who may or may not buy into one or more the naturalistic or supernatural  pro-authenticity scenarios that so dominate the world of  "sindonology" and its attendant media circus).

I may tack some more on later, if the HNO3 fails to arrive today, like the numerous boxes that my fumigation model ticks (which doesn't make the hypothesis compelling - merely plausible - but as I've said before, that's the prime raison d'etre of the scientist in my view - to generate hypotheses that are plausible, and then turn them into working models for TESTING.



Late addition (11 April): for the attention of Adrie van der Hoeven

Nitrated cellulose can "leak"nitrogen slowly or explosively

Sunday 12 April  (still waiting for nitric acid to arrive)

Checklist of reasons (work in progress) for thinking there may be some mileage in the nitric acid fumigation model. 

 (Having flagged up the possibility that some chemical changes might be due to oxides of nitrogen, NOx, instead of or in addition to HNO3, I'll refer now simply to the HNO3 model.).

1. If as I now suspect, the TS was an attempt to simulate a sweat and blood imprint onto "Joseph of Arimathea's linen", the latter receiving the traumatised and bloodied body of Jesus straight from the cross, then a chemical approach would have been the obvious way a forger/hoaxer would proceed.

 2. There was already a model of sorts for an image captured as a consequence of facial imprinting, namely the legendary Veil of Veronica, described by Neil MacGregor, until recently Director of the British Museum, as Rome's central icon in the mid 14th century. The presence of the vignette of a Jesus-like face above the word SVAIRE (Latin for face cloth) added to the Machy mould for a Lirey pilgrims' badge variant suggests that an attempt was being made to promote a whole body version of the Veil, arriving a little later than the Veil, immediately post-crucifixion.

 3. How to simulate ancient sweat (1300 years old in the mid 14th century)? It would need to look yellowed, rather faint, and, most important of all, would need not be imprinted (not painted). In other words the final image would not be like a painting, but what today we would call a tone-reversed photographic negative. Secondo Pia's remarkable tone inversion, 1898, is thus explained. 

4. One could use dye imprinting to produce that negative imprint, maybe using a corpse as template or even a life-size bas relief woodcut as suggested by Joe Accetta. However, might there be a less messy way of genberating an image that used a non-pigmented substance for the initial imprinting (allowing a living person to serve as template) and then expose that primary image to a chemical treatment that coloured up the imprint, leaving the background minimally altered. This kind of binary system allows for better control and fine-tuning of the end-result. One can take one's time with the initial imprinting, even doing in stages if desired, eg, head separate from torso. One can also seek to produce a final 'chemograph' by using the chemistry follow-up as a photographer used weak developing solutions, exposing for seconds, minutes even until the required effect was obtained, then adding a neutralising agent to stop the process in its tracks.

5. Neutralising agent? Like a base or alkali that is used to nautralise an acid? Might the developing agent have been an acid? The newly-discovered strong mineral acids, which today we call sulphuric (H2SO4)  hydrochloric (HCl) and nitric acid (HNO3)  were all the rage in alchemical circles in  13th century Europe onwards (the Islamic world probably knew about them sooner,  but the first clear recipe appeared under the (probable) pseudonym Geber, aka pseudo-Geber, thought by some to be the obscure Franciscan monk known only as Paul of Taranto). Might the new proto-chemistry and associated technology have provided a novel means of simulating the supersize-suaire?  Might our Paul of Taranto have been the 'brains' behind it all, whether or not directly involved in the actual hands-on fabrication?

6. STURP described the TS image as that expected of chemically-modified linen carbohydrate, citing as reaction mechanism: chemical dehydration, oxidation, and formation of conjugated double-bonds (the latter comprising the yellow-brown chromophores). Those changes it said could arise from thermal effects ("scorching") or, alternatively, from certain acids, notably sulphuric. Others too have speculated on a role for sulphuric acid, notably Joe Accetta, Joe Nickell and Luigi Garlaschelli.

I tested sulphuric acid and found it wanting: linen tends to disintegrate when intermediate concentration (battery) strength sulphuric acid is allowed to evaporate and concentrate on linen before there is appreciable browning. Hydrochloric acid, being non-oxidizing, is not considered as good a candidate for creating an artificial sweat stain as NITRIC ACID, which is a powerful oxidizing agent. Moreover, it is generally contaminated with the chemically reactive oxides of nitrogen, collectively known as NOx.  What's more the latter are formed when nitric acid oxidizes organic matter, so can arise as secondary products that add to the possible spectrum of  reaction products.

The alchemist known as Pseudo-Geber described in the 13th century the generation of nitric acid fumes from strongly heating a mixture of Cyprus vitriol (cpper sulphate), saltpetre (potassium nitrate) and alum (potassium aluminium sulphate). The fumes could be condensed in a water-cooled collection vessel to fairly concentrated nitric acid with variable water and NOx content. Thus was made something that approximated to our modern day nitric acid. An alchemist who spiltit on his skin would have observed an immediate strong yellow colour. It is not an acid "burn" as such, but a reaction between nitric acid and the aromatic amino acid side chains of proteins, giving the so-called xanthoproteic reaction, the basis of the quick laboratory protein-test. Might that colour change have provided the germ of an idea for simulating a sweat imprint on linen? Might limited exposure to nitric acid fumes also endow linen with an 'aged' look, over and above the ability to turn protein stains yellow?

Provisional model: one paints one's human volunteer or corpse with a viscous dispersion of starch, or white flour, or gum arabic, or milk, egg white etc - in other words an imprinting medium that is carbohydrate and/or protein.  The more gel-like the medium the better. One then covers with a sheet of linen and manually presses the fabric into and around the relief contours. The linen is then carefully pulled back, with its moist imprint, and then, with or without a drying step, is suspended in nitric acid fumes. It is withdrawn as soon as a distinct image of the subject appears against a lighter background.  The image is due to oxidized carbohydrate, possibly with a contribution from nitrated protein. One does not leave in the acid for longer than is absolutely necessary for obvious reasons. After removal the imprinted linen is dusted with powdered chalk or some other agent that neutralizes acid.

7. Fumigation might help account for the otherwise mysterious side strip. (The continuity of weave across the seam joining two sections suggesting that the strip was cut off, then ra-attached later). Might the side strip have been part of a strategy to ensure even coloration with no telltale evidence of temporary supports like poles. pegs etc.

8. Fumigation might account for image superficiality - if one assumes that limited contact to fumes affects the most superficial layer and components of the linen fibre, namely the primary cell wall (PCW) and its relatively open network of polysaccharides (the chemically-reactive hemicelluloses being well represented).

9. The blood first/iamge second chronology is explainable as follows: the subject serving as template was first coated with imprint medium (as above). Bloodstains were then added in all the biblically correct places. Then the combined image was imprinted, such that blood imprinted onto the linen first, residing underneath the imprinting medium.

10. The present appearance of the blood on the TS, looking too red for old blood, and being described as by Adler and Heller as "acid methemoglobin" is explained by by supposing that nitric acid and/or NOx had two effects: first, to oxidise the iron to the ferric state (Fe+3) and then to attach some kind of nitrogenous species to the iron as ligand (NOx?) A possible resemblance to the curing of ham and bacon using nitrites (NO2-, see Appendix below)  to make pink colours, as proposed earlier by this blogger, albeit  in a somewhat different scenario  (medicinal leech-stored human blood!) could serve as model, while noting Adrie van der Hoeven's inability to find closely matching spectral features. This one-time bilirubin specialist (mechanism of phototherapy for neonatal jaundice)  has previously voiced strong opposition to Adler's poorly documented proposals for implicating "trauma of crucifixion" bilirubin in the permanent red colour of TS bloodstains (bilirubin being notoriously unstable to light and oxygen as Adler himself later acknowledged in his recommendations for Shroud conservation) . 

11. Deterioration of a strong primary image to a fainter 'ghost' image is catered for, if one supposes that most or all of the imprinting medium flakes off over time, to leave an underlying remnant that is more intense than non-image background.

12. Fluorescence under uv? The Shroud body image is famously non-fluoresent, as I was repeatedly reminded when using hot metal "scorching" as a model. (I was not unduly perturbed, given that fluorescence means nothing centuries after the event: the fluorescent chromophores could have evaporated, oxidized, polymerized etc). However, an entirely different mechanism - chemical oxidation or even nitration by HNO3 fumes and accompanying NOx paints an entirely different picture, no pun intended.The products could be subtly different from those produced by thermal scorching. Alternatively,  the presence of accompanying hydrogen ions /protons from the acid could quench fluorescence.

Monday April 13

Sent this shirty email yesterday to Malcomxxxx, the name that Amazon gave for the retailer supplying the nitric acid  ( I placed my order 10 days ago, and pre-paid!)

Previously when I've ordered through Amazon, Malcolm, 

the goods have arrived on the start date for delivery. 

So I was most disappointed that my nitric acid did not

arrive last Friday or yesterday, and now wonder if 

I may have to wait as long as the last date 

(Wed 22nd! for delivery). Sorry - not good enough, 

not when one is paying over £6 for delivery. 

I had expected better of an Amazon retailer.

People who read my latest blog posting know I'm

waiting for nitric acid to test an important new idea

re the Turin Shroud.

http://colinb-sciencebuzz.blogspot.co.uk/

Kind regards

 Colin Berry

Update 13 April

Adrie van der Hoeven (comments) has suggested that Fanti's corona discharge hypothesis might account for the TS image. Here's a couple of images that says it cannot and did not (think hair) :

 

See comment number 25 addressed to  Adrie re Fanti's corona discharge theory.


Update: Tuesday 14 April

Have just stumbled upon this 1836 report on what nitric acid does to wheat flour versus wheat starch.

 It states that: "Nitric acid has the property of coloring wheat flour of a fine orange-yellow whereas it neither affects the color of fecula nor starch".

Interesting, very interesting. Yesterday I made a syrupy dispersion of wheat flour in hot water, using it to 'paint' my  brass crucifix, and then imprint a near-invisible image onto linen. 
 

Ready to paint crucifix with wheat flour dispersion in hot water, prior to imprinting the wet image onto linen.

When the nitric acid arrives (!) the linen will be suspended in the fumes. It would be most heartening if the nitric acid were to selectively colour, say, the proteins of the flour and the reactive hemicelluloses of the linen PCW, while leaving starch and cellulose relatively uncoloured.* Might one see a yellow TS-like image against a faint yellow-brown background of slightly and superficially oxidized linen? 

* Being uncoloured would not necessarily mean those white polysaccharides were chemically unaltered. Glycosidic linkages between the glucose units (alpha- and beta- in starch and cellulose respectively) could be hydrolysed by acid/water causing partial depolymerization, as seems to have been the case in my earlier sulphuric acid experiments, in which the linen fragmented under tension while remaining relatively white.  The nitric acid model might account for the observation that Shroud image fibres were more fragile than non-image fibres in Rogers' sticky tape sampling, though some qualifying assumptions would be necessary, e.g. that any starch or other paste used for imaging allowed greater access of nitric acid to the fibre cores, maybe via simple moistening effect, giving more water in which acid could dissolve and accumulate.

Update: Tuesday 10:45  Have just made imprints using (a) egg white and (b) egg yolk (the latter being an approximation to the egg tempera used before Renaissance- era oil paints as a vehicle for powdered pigments. 

Am now feeling badly let-down by the Amazon system that allows suppliers to quote hopelessly unspecific delivery times with 12 day windows, and who fail to respond to one's emails. Where's the customer service  especially when delivery costs are as much or greater than the value of the article itself?


Update Tuesday 08:46:  have just had this terse email:

no its in transit to you  nitric has been held up over

new rules but now sorted

Update: Wednesday 15 April

Still no nitric acid (am).

Discovered yesterday that my specialist (largely dormant) Shroud site with WordPress has an out-of-date banner.  It made reference to my earlier hypothesis linking thermal scorching off a heated template with the Templars (a scorched-on image being symbolic of the slow-roasting of the Templar leaders - Jacques de Molay, Geoffroi de Charney etc- at the stake in Paris, 1314).

While the direct thermal scorch hypothesis had a lot in its favour, despite any number of attempts to debunk it with crassly-designed experiments guaranteed to "over-scorch", there was one major drawback: one cannot easily monitor the degree of scorching to get the optimum end result. It all tooeasily fails the Goldilocks test (not too hot, not too cold).

The new chemical hypothesis being proposed in its place, based on chemically rather thermally-induced oxidation, albeit with similar end results in terms of carbohydrate caramelization etc, does not suffer that disadvantage. Colour development by exposure to chemical fumes, probably HNO3, allows for colour development to be under minutely-observed second-to-second control. If using HNO3 fumes from a chemical reaction between heated metal salts, it also used what in the 13th/14th centuries was state-of-the-art medieval alchemy - surely a point in its favour, and explaining the failure of we modern day science bods to have spotted sooner the application of long obsolete technology.

I have just this minute replaced the banner with the following:

No, a superficial image on linen, least of all a negative imprint, need not defy conventional science, and is not an excuse for conjuring up flashes of radiation or sub-atomic particles from a 2000 year old corpse. Let’s consider the capabilities of medieval technology – or even alchemy.

Update 17:00, April 15: email message through Amazon from nitric acid supplier:

"it is in transit to you I am trying to find out when"

My reply:

Thank you. You do realize, don't you, that my wife and I are prisoners in our own home,

 not knowing when the acid will arrive? 

This is quite the worst Amazon experience we have had in some 10 years or more. 

It's a form of slow mental torture. Why don't you tell me where you are, 

and let me drive over and collect? I'll happily pay twice to be spared this nonsense.

Kind regards

Colin Berry

Update 08:00 Thursday: new email message from nitric acid supplier:

yes sorry for that but we are sorting out courier 

like amazon do soon sdo you are emailed when it will arrive

My reply:

OK, but it will have to be delivered by the latest date you gave us (Wednesday 22nd April). Why? Because we are travelling after that date, and I'm not willing for nitric acid, no matter how well packaged, to be left with a neighbour. In fact, I doubt whether that would be legal anyway, given its hazardous nature.

Am now looking forward to your email (as are a lot of folk who follow my blog  and shroudstory.com who are keen to know what I find with nitric acid). As a teenager, I was able to order acids and other hazardous chemicals from my local pharmacist and take delivery over the counter. Happy days. 

Kind regards

Colin Berry

Update 20:30, April 16

Sent this email:

Could you be more definite about three things please?

First, have you already given the 1 litre of 70% nitric acid 

to a courier, or have you not done that yet?

Second: are you absolutely certain I will be sent an email

in advance, specifying the delivery date?

Third: can you confirm that I will receive the acid

by 6pm, Wednesday 22nd April (the latest day agreed for delivery)?

Thank you

Colin Berry

Back to the science: there's another constituent of linen that needs consideration in the fumigation model. It's lignin.

Lignin has lots of condensed aromatic rings and is a known target for nitration. So there are 2 dovetailing approaches. The first is to examine linen fibres under the microscope before and after fumigation with nitric acid. Might the lignin take colour, and if so serve as a potential signature for exposure to the proposed fumes?  Second, it would help to have a more lignified system as a reference. The obvious one would be a fibrous woody tissue, but that would not lend itself well to a more realistic "image imprinting", Solution? Imprint with a mush of crushed pear flesh? The gritty bits in the fruit are stone cells - clumps of lignified cells.  How will they look under the microscope before and after exposure to nitric fumes?

Update: 18:00 Friday 17 April

Halleluja: The nitric acid has arrived. (I was out when it was delivered so had to collect if from Post Office, after waiting 2 hours for our regular post-lady  to return it to depot undelivered!).

Experiments are under way.  Results initially promising (there being no immediate effect of HNO3 fumes on linen) but then disappointing (no immediate effect of gelatin or flour imprints either). Never mind. These are early days. Maybe it's the liquid acid solution that's needed for development of image, a quick dip maybe, rather than exposure to fumes. Will report preliminary results in a new posting.

Update Saturday  18th April 2015 (for me a red letter day!)

Seems I spoke too soon. The imprint from the hot-water dispersion of wheat flour was left exposed to nitric acid fumes overnight, and removed from its jar this morning for close inspection.

Imprinted image of brass crucifix onto linen, using viscous gelatinized wheat flour, air dried, then developed overnight in nitric acid fumes. (Photo autocorrected in MS Office Picture Manager).

There IS  a faint yellow brown imprint of my brass crucifix, and what's more it's against a beige background (the linen having acquired what might be described as an aged look). What's more there's virtually no imprint visible on the reverse side of the fabric! We have ticked a number of important boxes it would seem.

Update Saturday 21:15

Effect of overnight exposure of linen versus cotton to nitric acid fumes.

More to follow (possibly)?




Update Sunday evening 19 April

Maximal nitration of cotton finally produces nitrocellulose or gun cotton, which is highly combustible (needing no source of external oxygen to decompose rapidly - the nitrate presumably supplying oxygen if needed) What about partial nitration of linen.  While it would not be expected to produce explosive 'nitrolinen', it might, just might, make it more sensitive to heat (like hot pokers, fires in cathedrals?). Are you thinking what I'm thinking?

Here's a quick experiment I have just done comparing the effect of heat (from a ceramic hob) on (a) untreated linen (b) linen exposed to nitric acid fumes overnight. Both were then washed and air dried.

You can see one experiment in progress, with control linen (left) and nitric acid treated linen (right). You can also see the result of two completed experiments.

Conclusion: fumigation with nitric acid renders linen more vulnerable to charring. Might we have an explanation for why the Shroud of Turin has been so 'accident prone' where sources of external heat are concerned, even when inside a silver reliquary with limited oxygen? Are we seeing further evidence that the Turin Shroud image was fabricated using  early alchemical technology that employed nitric acid fumes?