Showing posts with label oxidation. Show all posts
Showing posts with label oxidation. Show all posts

Monday, April 6, 2015

Might fumigation with nitric acid vapour and NOx gases have been used to artificially age the Turin Shroud? Just an idea at this stage.

Chemical prologue (for those with limited chemistry, this introduction can be ignored down to the REAL INTRODUCTION below).

 
Discovered on googling (nitric acid stains clothes). Click to enlarge.

OK, it's a bit small. What it says is "Spilled some dilute nitric acid on my clothes in chem lab, is there any way to get the yellow stain out?"
My answer (here only): "Nope, except maybe in the same chem lab (using sodium dithionite  for instance as reducing agent to convert to a near colorless amine)."      

                                 R-NO2  + 6[H] -> R-NH2 + 2H2O

Or one could go for the diimide reagent (nascent NH=NH) that Adler and Heller finally resorted to in order to achieve bleaching of the Shroud body image (lesser reducing agents having been found wanting, at least the ones that were tried - although apparently not dithionite).   Correction: 12 April:  Nope. On reading I find that diimide is very specific in its action, targeting -CH=CH- double bonds for hydrogenation to -CH2-CH2-. I was wrong to assume that it would reduce R-NO2 to R-NH2.

REAL INTRODUCTION

One of the curious features of the Shroud is the exceedingly weak contrast between the body image and the background. It's said one has to stand 3 or 4 metres away to discern the image...

Shroud of Turin (from the Turin custodians' own site)



The image colour appears to be an intensification of the background colour, rather than a distinct colour in its own right.  This has led to comments like "image formation is the result of accelerated ageing of the cloth". It's easy to say, but is it true, and if it were, what possible mechanism could be operating to make an image behave in that manner?

Then there's the logistics that any medieval forger had to address in order to pass off a 14th century length of linen  as 1st century. Surely the cloth would have to be artificially aged, but how? If one knew how, then it might be possible to conceive of an imaging system that accelerated in the body image area the chemistry of what was happening in the larger non-image area.

It was a problem that Luigi Garlaschelli addressed in his modelling of the TS image by capturing and imprinting images off live volunteers by powder frottage and variants thereof. He pre-roasted linen in a heated  oven  and there was additional roasting later after application of powder (or slurry). Straightaway one can see how "accelerated ageing" becomes possible in a forgery scenario. Conceiving of a mechanism is a pro-authenticity scenario is another rmatter.

G.Fazio is another author who makes frequent references to the development of colour in background as well as image, with "latency" and "stochastic imaging" being referred to constantly (though I suspect I am not the only one to wish that he would enlarge some more on precisely what he thinks is happening on a physical, chemical and biological level).

More recently, the Dutch sindonological scholar and pro-authenticist Adrie van der Hoeven has devoted a vast open-access paper - some 260 pages no less- to the question of the Shroud blood that is "too red". Her solution? She proposes that the cloth had been impregnated before use with an extract of a yellowish dye (madder), and that blood subsequently mordanted to that dye to produce the permanent colour we see today, 2000 years later (in her view). There is much about that paper and its claims I find interesting and perplexing at the same time, despite (or because of) the wealth of documentation. I only mention it here as yet one more instance in which there has been a focus not only on the image characteristics, but on the phenomenon of a 'pre-conditioned' background for that image. I'll be returning to Adrie's paper again, probably in the third posting in this 'nitric acid' series.

So the question of dual colour, maybe of the same provenance but occurring at different rates, or maybe something more complex (two different mechanisms that just happen to look the same) cannot be avoided.

I propose to address it in two parts, using my new model (see posting immediately previous to this one) - namely the HNO3 (and NOx) fumigation model, and to address background colour first, then image colour, and see if linkage between the two, albeit at different rates OR extents, can be rationalized.

Let's take the Garlaschelli model as our starting point. Heating linen in air to get a discoloration almost certainly involves oxidation. What's more, infrared and other spectral analysis of Shroud image AND non-image areas  has detected the kind of functional groups that are consistent with oxidation, namely carbonyl functions (  ) etc,

But is atmospheric oxidation the only means of oxidizing organic compounds?

Answer: most definitely no. The common mineral acid studies in the last but one posting - sulphuric acid - is an oxidizing as well as dehydrating agent   - but only when its close to its maximum concentration (98%) and HOT. But there's another common mineral acid, namely nitric, HNO3, which is oxidizing over a much wider range of concentration, and which importantly can act at low temperatures too, albeit more slowly that hot. As the previous post relates. nitric acid was known as early as the 13th century in Europe. What's more, it was first prepared in vapour form, albeit contaminated with oxides of nitrogen, by heating a particular mixture of solid mineral salts (nitrates and sulphates) at high temperature. Might the fumes from that reaction have been used to artificially age linen as a first step in faking a 'relic' without even bothering to condense the fumes as recoverable liquid ("concentrated nitric acid" + NOx contaminants).

I propose that the linen was suspended horizontally in a pit (probably) over a retort that was generating fumes from the aforementioned  reaction mixture.  It was withdrawn when the linen was judged the right aged-look colour. (The body image - next posting- may or may not have been exposed to the fumes at the sane time).

So what's the chemistry?  Oxidation of sensitive carbohydrates, especially the more superficial ones of the PCW, could account for the background colour. We'll deal with the spectral analysis later (a tricky area, one I'm not looking forward to, but the nettle will have to be grasped). However, there's a second way that nitric acid can operate, especially when it's concentrated and/or relatively water-free in the vapour state - namely by nitration of protein, notably of aromatic amino acid side groups. Tyrosine is the one that dominates the literature, but tryptophan and phenylalanine occasionally  figure too.

Here's a schematic diagram of the end-result of nitration  (e.g. substitution of NO2 for H) of tyrosine in a protein.

Nitrated tyrosine side group in a protein - colour coded


There are two systems where protein nitration occurs to make a yellow colour - one wll known, one less so, except to clinical biochemists.

Concentrated nitric acid acid quickly does this to unprotected skin. It looks like a burn, but is in fact a xanthoproteic reaction to produce nitrotyrosine and other nitrated proteins that are bright yellow in colour.

The other, which I merely flag up at this stage, is the modern focus on nitrotyrosine as a marker for the overproduction of active oxygen and nitrogen species in a range of disease conditions. on which there is a growing literature. In brief, the gas nitric oxide, NO, is an important regulator in our body tissue. affecting for example the tone of smooth muscle in our arteries and thus blood pressure. However, an excess of NO can react with the active oxygen species superoxide,  O2-,  to form the peroxynitrite , ONO2-,  which can then attack a number of sites including the tyrosine residues of proteins, forming the same nitrated entity that caused the yellow skin in the above photograph. Should my current hypothesis ever find traction (these are early days)  be prepared for some pro-authenticists to seize upon in vivo nitration as a marker for what I call crucifictional physiology, comparable to Adler's outrageous ideas on 'trauma bilirubin', mere airy-fairy speculation that far too many, the STERA president included, tout as if established fact.

Enough of the chemistry. Let's look at more practical details of what's being proposed. Might the Shroud linen have been fumigated before acquiring the body image in order to give it an aged look? If so, how would that have been achieved in practice to ensure an even coloration, with no tell-tale defects that would arouse suspicions?  Let's imagine that a pit was dug into the ground, into which NOx and nitric acid fumes were led from a chemical retort, and that a pole had been placed or inserted over the top on which to peg or drape over the linen (later covered with a lid of some kin or large sheet (or sheets) of glass through which to check on progress. There's a problem. Pegs, if used, would have protected part of the linen, leaving pale areas that look like 'negatives' of the pegs. If draped over, there would also be a contact zone that was protected from the fumes.Might we perhaps have a novel explanation for the Shroud's mysterious so-called 'side-strip', or 'selvedge' as referred to by Adrie van der Hoeven. It's just visible in the photo at the top of this posting as a faint line extending horizontally from the corners of the cut-out portions of the fabric, some 8cm across its small dimension. It's in fact a seam that can be unpicked. Importantly, it's the same fabric both sides of the seam.

Anyone who's anyone in Shroudology has pondered on that side strip and offered opinions, and there's no time to discuss them all. Let's take just two of them. First, there was Bernard Power's. He thought the Shroud linen's width was too wide for the slab on which the body of the crucified Jesus lay in its rock tomb, so part of it draped vertically over the side facing the viewer. He proposed that an 8cm wide strip was removed from the edge of the long dimension (i.e. 4.4m x8cm) and then sewn back onto the opposite side.

Adrie rejects that explanation, claiming that the continuity of weave both sides of the seam is too good for Power's scenario to be true. She claims the strip was cut off, then immediately re-attached by stitching. Why would anyone do that? Her explanation? What we called the Shroud linen was originally intended to be a garment, and 1st century Jewish/Pharisaic law required that garment cloth had at least one seam.

I have a rather more mundane explanation, which can be accommodated to Power's side-to-side switch OR to Adrie's in situ detachment/re-attachment. Let's suppose the Shroud linen had been pegged out and fumigated, and then the unsightly peg marks discovered. Solution: cut off and discard the border with the peg marks, and replace with the same width cut from the opposite side. How will one explain away the seam? We'll come to that in a minute.

In the Adrie scenario, the problem of peg marks was foreseen. How can one suspend the linen in fumes to get even coloration without peg marks (or pole-marks)? Answer. Cut a strip off the edge, then re-attach loosely by lengths of strong thread, and use those threads to support the linen  - main section and strip - during fumigation. Later, the bridging threads are removed and the strip re-attached.

How to explain the border with the seam? The Lirey Pilgrim's badge, circa 1357, issued to commemorate the first undisputed exposition of the Shroud in a tiny French hamlet provides the answer, It is being held out vertically for display by hands that can an be seen gripping the edge. The owners of those hands are missing, due to that part of the badge being missing, but the Machy mould for a second Lirey badge shows the hands are those of men in clerical attire. It would have been an easy matter  to explain why there should be a segregated part of the Shroud set aside for gripping manually, citing reasons to do with this or that practical consideration for safe or respectful handling of an allegedly 1300 year old burial shroud.

There;s another practical aspect that needs addressing: the suitability of using a strong oxidising acid and its precursors (NOx) to age linen. Wouldn't that damage the fabric, making it later prone to disintegrate, comparable to the effect that evaporating sulphuric acid had on linen (not cotton) in my recent experimentation (see last but one posting)?

There's a big difference between sulphuric and nitric acids. Soak linen in dilute sulphuric acid, and will still look wet days later, and indeed is wet, as can be confirmed by touching (then quickly rinse off with runnin g water). Why is that? It's because dilute sulphuric acid becomes more concentrated on evaporation, due to evaporation of water, while the relatively involatile H2SO4 stays behind. That is far less likely to happen with nitric acid - HNO3 being more volatile (prone to evaporate) than H2SO4.


Boiling points: nitric acid: 83 C.  Sulphuric acid: 337 C.

Even pure sulphuric acid has a vapour pressure of less than 0.001 torr at 25 °C and 1 torr at 145.8 °C. (That's tiny, considering that a torr is a unit of pressure equivalent to just 1 mm of mercury in a barometer. Typical atmospheric pressure is a whopping 760mm mercury).


Even if there were traces of HNO3 left in the cloth days or weeks after fumigation, there are chemical mechanisms too that remove it. HNO3 is prone to decompose, not only when heated but when exposed to light. It breaks down to gaseous end-products that can escape:

4HNO3 (liquid)  ->  4NO2 (gas) + O2 (gas)  + 2H2O(liquid) 

(Terms in brackets indicate physical states at normal temperature and pressure).

As the above process occurs the acidity will gradually decrease. But in any case, the ageing process on fumigation would have been closely monitored to achieve minimal discoloration only . That would have limited the amount of unreacted nitric acid left in the fibres of the cloth. It's not inconceivable either that the treated cloth would have been treated with an agent or treatment known to neutralize and decontaminate acid, e.g. a light dusting with chalk. (There we have, in passing, an alternative explanation  for the allegedly high levels of calcium on the TS).

OK, that's do for now. The next posting(s) will be asking if and how the body image could have been imprinted using HNO3/NOx  chemical technology as well, either subsequent to pre-ageing of linen, or even simultaneously. At some stage the known visible and infrared reflectance spectra of the TS image and background will need to be matched against available literature values (limited!) for yellow nitrated tyrosine and other aromatic amino acids in proteins. We'll then need to consider what the target proteins are or were.

Here's a screen shot preview for starters (the full version is behind a paywall). It's the infrared absorbance spectrum of free nitrotyrosine (in acid) versus tyrosine. Click to enlarge.



Personal credo of this retired science bod: we scientists exist primarily to propose plausible and testable hypotheses. I offer that as a plausible hypothesis, as indeed I offer my novel but as yet untested nitric acid/NOx fumigation model of the Turin Shroud. It may or may not stand up to testing. If it doesn't, I'll simply abandon it, and try to think of something else. Anything's better than simply resorting to "Oh, it had to be supernatural". My beef is not with the supernatural as such. It's with those who use pseudo-science to push their agendas (any agendas), or who simply have lazy minds, or who despise scientific curiosity (or "meddling")...

Finally, there have been many false dawns for this blogger since beginning his Shroud project at the tail end of 2011 (some 250 postings to date, here and on his main specialist Shroud site.  In fact there have been so many false dawns that he's occasionally felt the need to install  motion sensor night lights in his head simply to see where he's going 24/7, if only to avoid bumping into solid fixtures and fittings in the all-pervading gloom. Maybe the HNO3/NOx hypothesis will turn out to be yet another false dawn, like thermostencilling, thermal contact imprinting, Maillard-assisted imprinting, alum-mordant -assisted imprinting etc etc.

But kindly note one thing, .Joe Marino: he has not yet reached a dead end, as you so engagingly put it. There are always new avenues to explore, and NO - (that's NO the negative, not nitric oxide) invoking the supernatural is not one of them. Now that's what I call a dead end, at least in experimental/scientific terms. One shouldn't need to remind him of that.

Update, Tuesday 7th April

Response so far to the new thinking? Absolutely none,  despite posting the following to the shroudstory site two days ago. Yes - a complete silence reigns. It's eery!

April 5, 2015 at 8:42 am
The timing is unfortunate (this being Easter Sunday). However, having spent 3 years in attempting to suss out the peculiar TS image, and been told by fellow scientists (well, some at any rate) that it has to be “supernatural” I can scarcely contain my growing conviction that a solution is finally within reach. A hint was provided in the previous comment or two. The question is: how to communicate the new idea? A fait accompli set out point by point? Sorry, not my style. I don’t do fait accompli Science works by hypothesis, experiment, interpretation, modification of hypothesis etc etc. There’s no room there for springing a fait accompli on folk. Better to build the story in easy instalments, ones that address the many disparate peculiarities of the TS image that have to be accounted for. (The new “hunch” could of course be wrong, and quickly demonstrated to be so, given it is capable of immediate testing by existing means were there free access to the Shroud. But there’s not, and indeed this blogger/retired biomedical scientist is not even able to wander into that Turin Cathedral simply to see the TS with his own eyes, so feels it’s not a huge and shameless imposition on folk, certainly on this ‘cutting edge’ site to say what’s in his mind, and to do so sooner rather than later.
There are two ways I can lift the lid on the new thinking. One is to post on my own site, and (no disrespect to Dan) hope it gets reported here with no details neglected or glossed over – detail being crucial in scientific research. The alternative is to drip-feed the new model here as a series of comments, as a continuation of this particular thread (why not, since Dan’s posting links to my site?) and not bother composing a posting to my own site until the feedback here has appeared. Might that not be a more internet-friendly and democratic way of doing things, while admittedly a far cry from the traditional route via peer-reviewed publication in journal articles (abstract only, cough up $$$ to get behind the paywall). What do folk think? Fait accompli on my site, or drip feed to this one?
Title for the new idea? How about: “A novel NOx/protein fumigation model for the Turin Shroud.” NOx represents the binary mix of nitrogen oxides (NO and NO2) that react together with water and oxygen to form nitrous and nitric acids (HNO2 and HNO3 respectively), or alternatively are generated in a reverse reaction when preformed HNO3 from a reaction mixture in a distillation flask dissociates at high temperature. Nitric acid reacts quickly with proteins that contain aromatic side chains (tyrosine, tryptophan etc) to form yellow ‘xanthoproteic’ reaction products. Both light sepia TS non-image background or darker, more intense TS image could be xanthoproteic reaction products formed by NOx fumigation of intrinsic linen OR extrinsic non-linen protein, or both. Several boxes can be ticked (e.g. lack of image fluorescence, even the Shroud’s mysterious side strip).
Comments invited re the best strategy for reporting a distinctly new angle on the TS body image – blood will have to wait until later. Happy Easter.

Further thought- 7pm Tuesday

Some might consider, with some justification, that too many eggs are being placed in the one basket. What if the spectral characteristics of the image and/or background do not fit with nitrotyrosine, or any other 'nitrated' entity? Does that mean having to abandon completely the nitric fumigation model (which has quite a lot going for it in general terms, as far as producing a 'ghostly' image is concerned). In fact there's at least one other chemical system/interaction that could deploy nitric acid, but which does not require protein or any other 'nitratable organic compounds. It uses green vitriol, known to medieval alchemists, and indeed conjectured to be the source of the first sulphuric acid. Green vitriol  is known today as iron (II) sulphate heptahydrate, i.e. FeSO4.7H2O, and I already have a large bag of it in the garage (it's cheap to buy as moss killer for lawns) and in fact used it 3 postings back to test out Joe Accetta's ideas re ink imprinting (the iron forms an intense black solution when added to extracts of plants tannins, like boiled/sieved pomegranate rind in my experiments - a substitute for medieval oak galls). Nitric acid turns green iron(II)sulphate brown. It's a simple oxidation of iron(II) to iron (III), or ferrous to ferric in the older system of chemical nomenclature. It might be possible to devise an imprinting medium based on iron(II) sulphate that is then "developed" by exposure to nitric acid fumes until the desired colour is achieved. Admittedly one would then have to find a way to remove the unreacted iron (II) while leaving the iron(III) in the fibres of the cloth,  but that's not impossible (washing etc).


Later still, 8:20pm  This posting with a video clip (which I'll view later) has just appeared on shroud story.com. It's a puff for Professor Fanti of Padua University and his claim, based on (dubious) chemical alternatives to radiocarbon dating, that the TS is much older than its apparent C-14 content would indicate. His new date range? It centres on 33BC +/- a few centuries either side. Well well.

But there's a snag, if one assumes for the sake of argument that my model is correct. Exposure to nitric acid fumes would wreck all his chemical clocks that rely on natural oxidation and ageing. That's especially true of the test, one of 3 as I recall,  that measures fibre mechanical strength. Two seconds of exposure to fumes might do more oxidative damage than two centuries exposure to atmospheric oxygen!  One could go further and say that the assumed correctness of the radiocarbon dating (1260-1390)  and the evidence for 'super-aged' fibres is supportive evidence for a manufacturing process that employed a powerful chemical oxidant. Sorry Prof Fanti.  You win some, you lose some, as every scientist knows only too well.


10:00 pm  One thing I've been keeping on the back burner while writing this and recent blogs is a hunch I acquired about a year ago as to the way the Shroud was supposed to be interpreted by the first cohorts of pilgrims arriving at Lirey. No, it was not meant to be seen as a "painting", as suggested by Charles Freeman, and certainly not executed as such. It was meant to be seen as a bodily IMPRINT (thus the negative light/dark reversed character) and, more specifically as a SWEAT imprint acquired when the NEWLY crucified Jesus was transferred from cross to Joseph of Arimathea's linen., the latter serving as a kind of makeshift stretcher or body bag or transport. Here's a link to a late Nov 2014 posting, just one of many on the sweat imprint idea:.

In other words, our medieval artisan set out to SIMULATE a sweat (and blood) imprint, and did so using the most up-to-date chemical, or rather alchemical knowledge available at that time, say late 13th to early 14th century. Tomorrow's post will flag up out some ideas about how that may have been done, using nitric acid fumes as a "chemical developer" for the artificial sweat to create what might be termed a 'chemograph', fumes that may have chemically modified the blood at the same time to account for its odd character ("too red" etc).

Who might have had both the alchemical technology AND the audacity to produce a fake relic that still holds millions in thrall to this very day?  The answer I believe is obvious. See the posting that precedes this one. The Shroud was I suggest the work of the Franciscan monk  Paul of Taranto, the same man as the one previously described as Pseudo-Geber according to some modern scholars. It was  made possible by Paul's technology for generating nitric acid either as fumes or condensed liquid. Whilst I've so far been able to find next to nothing about Paul the man, or even his birth and death dates, there's plenty on his philosophy and world view, and some of it looks very, very interesting.  Expect a posting at some stage that puts together these hunches, together with further findings for or against the hypothesis.


Update: Wed 8th April

Have just responded to Max Patrick Hamon on shroudstory.com with this:

Max patrick Hamon
April 8, 2015 at 4:41 am
Is it for convenience’s (or gross approximation’s) sake too you keep asserting a medieval super-genius

forged the TS image?
April 8, 2015 at 5:09 am 
In fact there is a possible candidate for that ‘medieval genius’ . Max, provided you accept an alchemist with a sideline in deep philosophical discourse. I refer to the 13th century (pseudo) Geber.
Geber, who in his day was regarded as an alchemist, and thus viewed with deep disapproval by the Church, had used Geber as a pen name (it’s complicated, being an attempt it would appear to pose posthumously as an much earlier Arab alchemist). However, a strong case has been made for identifying the pseudo-Geber as the Franciscan monk, Paul of Taranto.

Geber/Paul are credited with the first clear recipe for generating nitric acid and accompanying oxides of nitrogen by calcining a mixture of metal nitrates and sulphates, initially in the form of fumes from the reaction vessel. I am coming round to the view that those fumes could have been used to produce the image we see on the Shroud – as oxidation products of carbohydrates – and possibly even nitrated products of protein (yellow xanthoproteic products can be formed by nitration of aromatic side chains of tyrosine, tryptophan and phenylalanine).
See my most recent two postings for details.
(Links inserted)

Conc.nitric acid is on order. Rest assured I’ll be testing the hypothesis at the earliest opportunity, at some risk to my lungs.

Was this the man who supplied the chemical know-how for faking the Turin Shroud - 13th century Paul of Taranto?

Update 30 June 2015  Looking back through my older postings, I came across this one. Folk may be puzzled by the abrupt switch from sulphuric to nitric acid with no reasons being given. That's because I had been using the Comments facility on a different site to hint at a rapid sea change in thinking.



The caption reads: "Paul of Taranto was a 13th century Franciscan alchemist and author from southern Italy. Perhaps the most recognized of his works is his Theorica et practica, which defends alchemical principles by describing the theoretical and practical reasoning behind it. There is also evidence to suggest, however, that Paul is also the author of the much more widely known alchemical text Summa perfectionis, generally attributed to Geber (aka "Pseudo-Geber")

Here's the first known recipe (in precise detail) for making nitric acid fumes (which might, just might, have been used to produce the Shroud image via its propensity to oxidize and 'nitrate' (verb) organic matter, turning it sepia or yellow-coloured in the process).

"Take a pound of Cyprus vitriol, a pound and a half of Saltpetre, and a quarter of a pound of alum. Submit the whole to distillation, in order to withdraw a liquor which has a high solvent action. The dissolving power of the acid is greatly augmented if it be mixed with some sal ammoniac, for it will then dissolve gold, silver and sulphur"

Cyprus vitriol is copper sulphate, saltpetre is potassium nitrate, and alum is potassium aluminium sulphate. (Sal ammoniac is ammonium chloride, but is not needed to generate nitric acid).

Here's a mechanism that has been proposed for what happens when a simpler binary mixture of copper sulphate(CuSO4) and  potassium nitrate (KNO3) is heated to a high temperature (600 degrees C or higher). The chief end product, nitric acid, is shown in red ( HNO3)



2CuSO4  → 2 CuO + 2SO2 + O 2  

KNO3 + SO2 → KO3SONO

2 KO3SONO N2O3     + K2SO + SO3

If the cooling is insufficient, N2Odecomposes spontaneously:

N2O3  →  NO + NO2
or otherwise reacts with water:

 N2O+ H22HNO2

and the subsequent disproportionation of HNOproduces HNO3 :

3HNO2  →  HNO3  + 2NO + H2 O
 
Oxygen produced in the first reaction oxidizes NO:

2NO + O2  →  2NO2

and the dissolution of the resulting oxide in water yields further nitric acid:

4NO+ 2H2 O + O2  →  4HNO3


 These days the reaction is accomplished faster and more easily by heating a mixture of potassium nitrate and concentrated sulphuric acid, H2SO4, in a glass retort, or other all-glass apparatus, i.e. no corks, rubber bungs or other organic matter.




The nitric acid collects as a liquid in the cooled receiving flask on the right. It will be yellow or brown due to dissolved nitrogen dioxide (an impurity). There may be other oxides of nitrogen too (thus the references to NOx to avoid being too specific)

So what's this got to do with the Turin Shroud? 

 I propose that the Turin Shroud  image may have been formed by a reaction between nitric acid and/or nitrogen oxides (NOx) acting upon organic matter, notably carbohydrates (oxidation) and even protein (nitration). It may even account for the blood that is "too red".

I provisionally call it the HNO3/NOx fumigation theory.You read it here first, correction - second. I dropped some hints yesterday on shroudstory.com. (See later comments). The key concept is that of fumigation, note, with relatively little liquid water. Details to follow in the next days and weeks (nitric acid  is on order for a new round of acid experimentation, close on the heels on my H2SO4 mini-project - see the posting immediately preceding this one)

Methinks that'll do for now. I'll give details in future postings, and suggest how the hypothesis can account for a considerable number of Shroud characteristics (the latter collectively earning it the description "enigmatic") and potentially be tested, possibly  falsified. Please note: it's just a hypothesis for now: my interest is less to do with debunking the authenticity of the Shroud, and more to do with trashing the absurd notion that the Shroud HAS to be of supernatural origin. See that woeful article in the Independent, December 2011, the one that prompted this blogger/retired biomedical scientist to go 'mixing it' with the purveyors of pseudo-science.

Further reading:

On Pseudo-Geber/Paul of Taranto: preview of  William R.Newman's critique: 




Thursday, March 19, 2015

Towards a new, more chemically-nuanced model for the Shroud of Turin (with hat tip to STURP’s Joseph Accetta). Think slow-release H2SO4, and maybe iron catalysis too.



 
 
*
There's generally scope for fine-tuning models in science...


Summary: What we see today is not what the putative 14th century fabricator of the Shroud intended us or rather his contemporaries  to see. The Mark1 image was a more prominent dye/mordant combination, essentially as proposed by STURP's Joseph Accetta, imprinted onto linen possibly to resemble dried, ancient sweat (with blood pre-additions too). (See earlier ideas onthis site re the Shroud being an attempt to produce a life-size rival to the fabled “Veil of Veronica”).  That Mark 1 Accetta image has largely if not entirely disappeared, as a result of natural wear and tear, bleaching by sunlight, detachment of mordant etc etc, possibly even laundering. What remains is a Mark 2 ghost image, still a negative “photograph-like” imprint, one that formed gradually under the dye mordant via chemical action that mimics the effect of scorching with a hot metal template.  The chemistry would be similar (dehydration, oxidation of linen carbohydrates) but achieved slowly at environmental temperatures by chemical reaction with or without catalysis. 

The chemicals used in medieval bleaching offer ample scope for modelling of slow superficial “scorching” of linen fibres, especially the acid mordants like aluminium and iron sulphates that easily hydrolyse initially to dilute sulphuric acid. The latter becomes steadily more concentrated when exposed to air due to progressive evaporation of water, the sulphuric acid being relatively involatile. and increasing concentration to largely anhydrous H2SO4 with a powerful dehydrating, caramelising and finally charring action on carbohydrates is well. Caveat (an afterthought):  It never becomes standard "concentrated" sulphuric acid (98%) however, which is what I call "The Beast" give its violent affinity for water, as witnessed by its ferocious charring of carbohydrates (see  photograph below). Why not? Because maximally concentrated 98% H2SO4 is highly hygroscopic: it picks up moisture from the air, increasing its volume considerably as it does so. It's self-evident therefore that dilute sulphuric acid can never evaporate all the way down to the 98% level when exposed to the air (ordinary moist air that is). It simply becomes more concentrated - though I can't as yet put a figure on it.



This is what concentrated sulphuric acid does quickly to cotton (wiki).  This blogger has placed an order for modern car battery acid (37% H2SO4) which will be used for observing the time-course on linen as water gradually evaporates off to leave conc. H2SO4. Might one see subtle sepia-coloured caramelization rather than charring? (Update: yes, but barely perceptible  if tested at room temperature: elevated temperatures are needed for clearly visible browning).

Catalysis of oxidation by iron salts is an added possibility, given the ability of variable-valency iron salts (Fe++ and Fe+++) to facilitate organic redox cycles, acting as intermediary electron acceptor/donors between atmospheric oxygen and oxidisable substrate.The traces of iron oxide that Walter McCrone and his microscope detected on the Shroud may not have been artist's red ochre, as was proposed, but oxidized iron mordant, e.g. iron (III) oxide-hydroxide, FeO(OH).H2O, more commonly written as Fe(OH)3. See the wiki entry.

More to follow (much more!) in short time-spaced instalments. Sorry, it's the way I work.


Still Thursday 19 March,  11:50

Sulphuric acid, H2SO4, the  most common mineral acid of commerce, with thousands of applications, has always lurked in the Shroud literature. Take this extract, for example, from the 1981 Summary of conclusions from the Shroud of Turin Research Project (STURP):

Quote (STURP 1981) : The scientific consensus is that the image was produced by something which resulted in oxidation, dehydration and conjugation of the polysaccharide structure of the microfibrils of the linen itself. Such changes can be duplicated in the laboratory by certain chemical and physical processes. A similar type of change in linen can be obtained by sulfuric acid or heat. However, there are no chemical or physical methods known which can account for the totality of the image, nor can any combination of physical, chemical, biological or medical circumstances explain the image adequately.


Sulphuric acid pops up again in that stunningly original and inventive attempt by Professor Luigi Garlaschelli and his students to model a Shroud-like image.  I shall look out his paper (a copy of which he sent me personally) and quote a few of his own words. In the meantime, here's a comment I left on Dan Porter's shroudstory site last summer that is highly germane to what follows:

July 17, 2014 at 3:13 pm
Luigi Garlaschelli’s powder-rubbing model, even if incorrect, gives a pointer to the kind of subtlety that is possible if wishing to leave a “stamp” (good, straightforward term)
on linen.
He proposed that the kind of ochre (red-brown ferric oxide, Fe2O3, available in medieval times, made by decomposing green vitriol, hydrated ferrous sulphate, FeSO4. 7H2O), would have contained acidic impurities, notably sulphuric acid, which becomes conc H2SO4 when one drives off water.

He reckoned that the acidic ochre was used to produce a negative image from a human subject, and the linen then heated in an air oven to make it seem older than it really was. But the heat might also have caused the acidic impurities to chemically etch the linen, via the same kind of pyrolytic chemistry (dehydration reactions etc) that occurs when linen is scorched directly with a hot metal template. Later the solid ochre flaked off, or was scrubbed off, leaving just the ghostly image (Hugh Farey has also flagged up this kind of erosion scenario as a possible explanation).

In other words, there’s a mechanistic spectrum that runs between a purely thermal action (scorching from a hot template) or a chemical mechanism (traces of sulphuric acid etc) or any number of in-between mechanisms that rely on a combination of chemistry and heat.

Despite these uncertainties re precise mechanism, the narrative may hinge on the credibility or otherwise of a medieval artisan asking himself a simple question: “How can I produce a whole-body version of the Veil? How can I simulate a post-Criucifixion sweat imprint that might be left on linen as a yellow discoloration?”

It didn’t need to be a real sweat imprint – merely a yellow-brown image that could be represented as an ancient degraded sweat image.

My own preferred scenario is that of a post 1314 scorch-imprint designed to simulate a slow-roasted Knight Templar, possibly a Knight Templar (Jacques de Molay?) being “reinvented” as a sweat imprint of the crucified Jesus.

Then there was my stumbling for the first time on the unique approach of STURP's Joseph Accetta. PhD.
Yup, that's Joseph Accetta PhD, electro-optics/laser/imaging expert, not to be confused with another Shroud researcher - August Accetta MD.

Again, it saves time if I simply cut-and-paste a comment I posted to shroudstory in June 2014, with the key passage from Accetta's 2008 Ohio Shroud conference referring to H2SO4 highlighted in red:
 


June 5, 2014 at 12:55 pm
Try downloading this PowerPoint presentation from Joseph Accetta, David (he being the subject of a recent posting here, and one of STURP’s genuinely scientific, non-agenda driven, non grandstanding participants in my view).


Go to the last few pages (approx 24/25). There you will see model spectroscopic (ir) studies not just with thermally-imprinted scorches, but also with linen that has been chemically dehydrated with 36% H2SO4 and even your invisible ink (lemon juice).

I’d be the first to admit there may be little to distinguish between an image produced by chemical as distinct from thermal dehydration (especially if chemical action was heat-assisted – see Luigi Garlaschelli’s model ‘frottage’ imprinting with acid-contaminated red iron oxide). It’s the vehicle for acid that is important (not too runny, not too viscous).

Some of us eagerly await details of what JA will say at St.Louis. Let’s hope it receives more attention than his meticulous and detailed studies to date.

Nuff said. I’m thinking of doing a post dedicated entirely to JA (he being my kind of scientist).

Still Thursday, 12:50

We then learned that this STURP veteran was scheduled to present a paper at the October 2015 St.Louis Shroud conference. What would he say? What was his current focus, some 35 years on from that celebrated  week in intense activity in Turin?

Well, here was the abstract he submitted for the St.Louis meeting.


Abstract:

This paper is based on the assumption that the Shroud is of 14th century origins consistent with its radiocarbon date and thus must be explained within the technology and historical context of that era. Avoiding the controversy surrounding the date, the author presents a plausibility argument to reconcile its visual and forensic properties with extent 14th century printing technology, geographical circumstance and historical context. The observed 3-d properties of the image are discussed in relationship to physical image formation processes and a plausible explanation for this extraordinary effect is given based printing techniques known to exist at that time and in that locale. Further the argument is reinforced with analytical results showing that under any reasonable assumption about the surface bi-directional reflectance distribution function (BRDF) including the use of measured human skin data, the observed 3-d properties cannot be reconciled with any known radiative imaging process and thus must be a contact process. 
 No further) references (as yet) to H2SO4 note, But there was that intriguing allusion to "printing techniques". What was that about? Had anyone mentioned printing before (barring my preferred scorch imprinting)? Hadn't STURP excluded not just artists' pigments, but inks and dyes too? What did this Joseph Accetta have up his sleeve?

Here it is: Origins of a 14th Century Turin Shroud Image (pdf)

First, the disappointing feature. There's no further mention of sulphuric acid. Indeed, there's only a single reference when one searches "acid" - to tannic acid.

But acids, or at any rate "corrosive" agents,  are implicated, and importantly it seems, in this intriguing passage, one that sets the tone for an entire new slant (at least that this blogger is aware of) on the possible origins of the 'enigmatic' Shroud image:

"Iron gallate and carbon inks of which there are reportedly several hundred recipes are seemingly plausible candidates for coloring agents because they were the ink of choice during the medieval period and could be made sufficiently viscous with gum Arabic, linseed oil or a number other binders to serve as suitable colorant for textiles. It should be noted that the penetration of the colorant into the textile was not a primary consideration during the printing process because mechanical stresses would have flaked almost all of the ink away. Many of these formulations are corrosive and would have over time either caused cellulosic degradation or reacted with some other substance on the linen such as a mordant or starch.  Some of these inks are known to create time dependent contrast effects depending on the formulation and there are several hundred papers dealing with the conservation issues on rare documents relative to these inks."

So what are these corrosive agents? Are they the dyes themselves, or the mordants that attach them to cloth? Why would corrosive action be necessary? Dyes are dyes, surely, that can be used to imprint an image without having corrosive action, the latter being unnecessary and undesirable surely?

Accetta has also put his St.Louis slide presentation online.


There are details there that are not in the pdf:








So the original image was prominent. What we see today is a degraded image. Presumably the corrosive ink (iron gall?) was corrosive and contributed to the degradation. Does that narrative fit with what we know about the TS image, notably the lack of reverse (aka obverse) side image? Would not inks or other soluble dyes penetrate, even if thickened with gum arabic or some other viscosity-increasing agent? Would not some of that cross-over have survived to be spotted and reported on by STURP and others?

Before addressing those issues in more detail, reference must be made to another slide in Accetta's presentation , alluding to work done by a French group on the stability of medieval documents written in the standard iron gall ink:

Here's a cut and paste from the slide:




FTIR techniques applied to iron gall inked damaged paper

REMAZEILLES Céline, QUILLET Véronique , BERNARD Jacky LEMMA, Université de La Rochelle

INTRODUCTION

Iron gall ink corrosion of paper is one of the largest threat for our graphic patrimony. A great work has been done in this field to explain the possible mechanism of paper degradation and to propose  curative methods  The main degradation mechanism proposed in the literature is the following : iron gall ink prepared with different ingredients including tannins and vitriol causes both acidic hydrolysis and Fe2+catalysed oxidation of cellulose. Paper turns brown and loses its mechanical properties. Yet the great variety of iron gall ink recipes , and the great variety of visual aspects of manuscripts suggest that many side effects could occur and contribute to the different aspects of paper degradation (colour changes, halos, mechanical properties). 
...

So, whilst one has to look quite hard, there are two additional gems of information in that French paper - first the reference to "vitriol"  (SULPHURIC ACID) lacking in the main presentation AND the recognition that iron salts are capable of catalysing redox reactions sufficient to oxidize chemically inert cellulose (though that need not be the target polymer in linen, despite being the major constituent - there being more sensitive ones, notably the hemicelluloses of the superficial primary cell wall).

Time now to put cards on the table. First, this blogger suspects that Accetta with some French back-up was right: the Shroud image began life as wet imprint - not the dry scorch imprint that has been my model thus far (though its proved handy in de-mystifying the negative image and, especially, 3D properties). Iron gall ink, with its mixture of plant tannins and iron salt mordants serves as a handy model for the imprinting medium - but no more. Any number of soluble dyes could have been used, probably mordant-assisted, e.g. with commonplace alum (potassium aluminium sulpahe) or with iron or chromium salts. But here's where I diverge from Accetta. He thinks the corrosive agents, whatever they might be (mordants? vitriol?) partially degraded the original image. leaving a remnant that we still see today. I beg to differ. I consider that the entire dye/mordant combination has vanished entirely, for a combination of physical and chemical reasons (crumbling away, bleaching by sunlight, loss on laundering, however infrequent). But we still see a 'ghost' image that is NOT the original. Here's a schematic as visual aid:



 
3 stages in formation of the present ghost image on the Turin Shroud, with disappearance of the initial more prominent dye/mordant image



What in a generic sense could have produced a secondary 'ghost' image, probably quite slowly, but fast enough (decades, centuries) such that when the primary Mark 1 dye/mordant image  has faded from a view a faint but STABLE ghost is revealed?

There are two candidates, close chemical cousins with similar properties, that are in the frame. One is alum, with aluminium sulphate as 'active ingredient',  that is well known for releasing SULPHURIC ACID in solution or exposed to moist air, due to chemical hydrolysis:

aluminium sulphate + water ->  colloidal aluminium hydroxide (the true dye-binding mordant) + sulphuric acid

Al2(SO4)3  +  6H2O  ->  2Al(OH)3 +  3H2SO4 
 
 (Aluminium hydroxide can also be regarded and/or named as hydrated aluminium oxide, the two being equivalent in terms of atomic makeup)




But there's the iron, at least in iron gall ink.  How did it get there? It could have been added as green vitriol, aka ferrous sulphate, aka iron (II) sulphate, FeSO4.7H20. There are other more rustic ways of introducing iron, even as elemental iron and crude vitriol (sulphuric acid). In time, it oxidizes in air to orange-brown ferric sulphate aka iron (III) sulphate. That plays different roles, depending on whether it's an adjunct for use with an ink (e.g. oak gall) or a plant dye for fabric printing. In ink, it helps give a darker colour, quickly visible. In fabric-dyeing it acts as a mordant, in addition to effects on colour, which can vary, and serves as a mordant for the same reasons as alum above. Why? Because it also undergoes an analogous hydrolysis in water, producing iron hydroxide, aka iron oxide-hydroxide, the true mordant AND again that ubiquitous SULPHURIC ACID that have can have other actions, whether intended or otherwise:




 Fe2(SO4)3  +  6H2O  ->  2Fe(OH)3 +  3H2SO4



Let's suppose for the sake of simplicity that a plant-dye had been used with alum as mordant. The mordant would have attached the dye firmly to the fabric, but not prevented bleaching and other deterioration of the colour over decades and centuries. Meanwhile any alum excess in the cloth could have slowly released sulphuric acid which , acting on the superficial linen fibres under the dye -coating, would (or could) have generated a ghost image , invisible to the first cohorts of pilgrim spectators. However, one is relying purely on H2SO4 to degrade the linen fibres. It can do that via chemical dehydration, at least in principle. But scorching of linen, whether by thermal or chemical means, is generally assumed to require oxidation as well as dehydration. STURP acknowledged as much in its 1981 summary. Maybe it assumed that atmospheric oxygen would produce the oxidation (cold sulphuric acid alone is unlikely to result in oxidation). But contrary to popular belief, atmospheric oxygen is not very reactive chemically, due to its triplet electronic state, which is why one has to raise temperature to kick-start combustion and other oxidation reactions. Organic compounds, even complex ones, can often survive indefinitely if there's no flame or other source of ignition. That's where iron salts come in handy if one is wishing to implicate atmospheric oxygen as the ultimate oxidant - they CATALYSE oxidative reactions, as those French workers recognized. Why? How?
Well, let's not turn this posting into a chemistry lesson. Suffice it to say that iron, unlike aluminium, can exist in solution as Fe++or Fe+++. The first can act as a reducing agent by donating an electron to an organic or other compound ( like linen carbohydrate!) become Fe+++, and the second as an oxidizing agent by accepting an electron. One can have s0-called redox cycles, in which iron shuttles between the two forms, using atmospheric oxygen to convert any temporary surplus of Fe++ back to the oxidizing Fe+++.

One would not be so focused on iron if it were not for the fact that Walter McCrone discovered flecks of iron (III) oxide on sticky-tape samples of Shroud fibres supplied to him by Raymond Rogers. He assumed it was artists' red ochre, and quickly dismissed the TS as a medieval painting. But the iron oxide's crystallinity suggested it was too pure to be artist's pigment (often ground up natural mineral in medieval times and thus impure). Might it have been iron oxide that formed from use of an iron mordant in dyeing, or, as Accetta would prefer, as an adjunct in oak gall ink or similar?
If iron had been present, for whatever reason, it greatly increases the probability of converting linen to yellow or sepia products resembling a superficial scorch, because the probability of there being oxidation as well as dehydration is greatly increased. What's more, the iron does not get used up if the redox cycle is linked to atmospheric oxygen  as ultimate electron acceptor, becoming oxide or hydroxide ions. In other words, the oxidation can be CATALYSED  by mere traces of iron that cycles between its two valence states. 

So we have a new model to explain why the TS image looks the way it does - faint, almost to the point of invisibility, at least close-up, because it's not the Mark 1 image we see, but a ghost left by acid and/or iron impurities in the putative dyes and mordant mixes. That ghost is a kind of chemically scorched or 'caramelized' carbohydrate.

Are there features of the Shroud image that are not explained?

Fluorescence under ultraviolet light, or rather lack thereof?

Fluorescence was always the Achilles heel of the dry thermal scorch imprint model. Thermal scorches fluoresce, we are told, at least the 1532 "scorch" margins on the TS, while the TS body image does not. What about chemically-induced scorches? Well, there's some confort to be had from Luigi Garlaschelli's modelling of the Shroud image, using metal oxides in slurry form with added acids (sulphuric included) as imprinting medium. The final images did NOT fluoresce (he was keen for us to know that).


What about image superficiality (allegedly 200-600nm in thickness )? What about ease of 'strippability' with adhesive tapes? What about mechanical strength of image-bearing fibres? What about the claimed blood first-image second chronology/ Can that be better accommodated in the H2SO4 and/or iron model? (yes, I believe it can). Nature of the template? Woodcut? Customised one-off, or one that if preserved would be recognized as consistent with art history or early attempts at fabric printing? Did it really need to be wood? Might not easily mouldable clay have been a more convenient material for a one-off, and then quickly hammered into small pieces, destroying the only evidence as to method of manufacture?

More to follow. But that's enough for one day methinks. Experimental testing? A start has been made, and more chemicals are on order (sulphuric acid, iron sulphates, gum arabic).

Freshly-prepared extract of pomegranate rind/pith, boiled down to thin syrup.

Having no easy access to oak galls, I'm using pomegranate rind/pith to make a syrupy extract of yellow tannins, with or without alum as mordant that can be painted onto bas relief templates to get imprints. (Yes, they are tone-reversed negatives, needless to say, and respond reasonably well to 3D enhancement). See the blog posting that precedes this one for preliminary results.

Friday 20 March

Before discussing anything else, let's see how this double imprint, fast dye/slow chemical scorch mechanism offers an explanation for that "blood first/image second" finding of Adler and Heller. I allude to their experiment with the protease in which blood proteins were digested off TS linen fibres with proteolytic enzymes to reveal colorless fibres underneath. That finding has always been an embarrassment for those of us who provisionally accept the radiocarbon dating, warts an' all (while wondering why there was no Phase 2 sampling from additional sites). How could a forger know where to paint on bloodstains if the linen had initially been image-free? OK, here's an explanation, or at any rate a get-out- of- jail-free card. The blood was NOT painted on first. The image was dye-imprinted, and the blood painted on top (the easy way). Then the Mark2 image gradually formed under the dye imprint, due to chemical action on the linen carbohydrates. But that did NOT happen where there was blood overlying the body image. Why not? Because the reactive chemicals (H2SO4, iron salts etc) had an easier substrate ON TOP than underneath with which to react, so were constantly mopped up by that overlying blood leaving the linen fibres in their original pristine condition. So when STURP scientists came along centuries later and digested away the blood to find those pristine linen fibres exposed, they quite reasonably supposed that the blood was acquired first, not second. They weren't to know that there had originally been a long-gone Mark1 dye-imprint between blood and Mark2 chemical scorch, were they?
Thought-provoking quote on this morning's BBC site under an article headed : "Can Religion and Science Bury the Hatchet?"

"'Simplistic' distinctions
 
"The old distinction that science is about facts and religious belief is about faith is far too simplistic," says Prof Wilkinson.
"Science involves evidence, but it also involves skills of judgement, and skills of assessing evidence.
"After all, you only have a limited amount of evidence to base your theory, and you have to trust your evidence - which isn't far from being Christian.
"It doesn't involve blind faith - and indeed religion is not good religion if it is simply based on blind faith.
"Christianity has to be open to interpretation about its claims about the world and experience."
For Prof Wilkinson, the two are absolutely not mutually exclusive."

Interestingly, just yesterday I came across a site for secondary teachers in England and Wales that has "Understanding Science 101" in the title bar (yes, really). There's some amazingly perceptive stuff in there that one rarely meets elsewhere. It should be required reading for anyone who is not a scientist, but thinks they know and understand how science operates and makes progress - or tries to, or who imagines that just anyone can do science. The expression "they don't know the half of it" springs to mind. This blogger is a 70 year old retired scientist, but is still learning more about dos and donts of research strategy with each new passing day. Might he have arrived where he is now but much sooner?



Back to practicalities: what about that suggestion from last night - using moulded clay instead of  Accetta's carved/engraved woodcut as template for dye/ink imprinting?

If clay, did it need to look like this?


It's taken from the Home Page of Rolfe's Enigma site (see previous posting for this blogger's view on those allegedly  'enigmatic' features that are supposed to equate on suspects with 'unique', but don't really). Yes, I realize I've been a bit mischievous in using that image, which in the Rolfe narrative would be a model derived from scanning the Shroud image, not a model used in reverse to make it! (We'll overlook the small matter of it having complete arms, as if there had been no 1532 fire)

Now then, if you, dear reader, had been a medieval artisan supplied with a cartload of wet clay and been told to fashion a life-size effigy of the lifeless Jesus recently taken down from the cross, would you have attempted to reproduce the above?  Suppose you had a rough idea about how the imprint was to made, e.g. by painting dye onto the highest features of the relief, then spreading linen on top, then manually pressing the linen into all the hollows and crevices to get best most intimate contact between template and fabric. Would you have then proceeded to mould (or attempt to mould) a fully 3D effigy. The answer is obvious - NO. It's impractical to do that. Wet clay, whilst stiff, would not allow one to do that - gravity would cause sagging of those parts not in contact with the supporting surface. But here's the crucial point. One does not need a fully 3D effigy. A bas relief is sufficient, or rather two, one for frontal, one for dorsal side, if one look  at the Shroud. There are no sides! Indeed, that's just as well, since any attempt to imprint off the sides of that effigy one sees above would introduce lateral distortion.

Take away message: not only was wet clay (later left to set) the likely template material. It was fashioned as two separate bas relief templates, one frontal, the other dorsal. That incidentally would account for why one is said to be some 7cm taller/longer than the other (the source of much 'creative accounting' on the part of the pro-authenticity tendency that need not concern us right now).

Might there be practical difficulties in imprinting off a clay bas relief template instead of woodcut? It's a moot point. I shall try to get hold of modelling clay and do some crude experiments to see how well the dye/mordant mix sticks to the template and how well it then transfers to linen. Having already experimented with metal templates in dye as well as scorch-imprinting, I'm not expecting there to be insuperable problems, especially as there's the possibility of making additions, e.g. soap or other wetting agents etc.that might improve the outcome.

It's the imprinting off a bas relief, or less probably fully 3D template that generates the image with negative (dark/light reversed) properties AND reasonable response in 3D-rendering progeams like ImageJ. It shouldn't be necessary to have to say this in 2015, but still we have to endure lectures from so-called historians (with amazing blindspots for the historical record) telling us the Shroud is just a degraded painting or that we have overlooked the effects of ageing, wear and tear etc.  (Not so. Some of us, notably Hugh Farey and myself have been exchanging views on bloodstain and image-fibre attrition for YEARS.) This might be a good point at which to slip in a couple of cut-and-paste items of historical interest and relevance.


Here for starters is the celebrated, some say suspect d'Arcis memorandum, kindly translated initially from the medieval Latin into the French you see here (red) and a DIY-makeover (black) of the Google translation. We're told emphatically by a self-styled academic historian that no one in the 14th century would have been taken in by claims for the Shroud being the authentic burial cloth of Jesus. Is that the impression one gets from reading this?

From the letter of Bishop Pierre d'Arcis, addressed to Pope Clement VII, residing in Avignon (Letter written in 1389):


« L’affaire, Saint Père, se présente ainsi. Depuis quelque temps dans ce diocèse de Troyes, le doyen 
"The case, Holy Father, is as follows. For some time in the diocese of Troyes, the dean 
 

d’une certaine église collégiale, à savoir celle de Lirey, faussement et mensongèrement, consumé par la
of a certain collegiate church, namely that of Lirey, falsely and untruthfully,  consumed by the 
 
passion de l’avarice, animé non par quelque motif de dévotion mais uniquement de profit, s’est procuré 
 passion of avarice, driven not by any reason of devotion but only of profit, procured

 pour son église un certain linge habilement peint sur lequel, par une adroite prestidigitation, était la 
for his church a certain cloth cleverly/cunningly painted on which, by a clever sleight of hand, was 
 
 représentée la double image d’un homme, c’est-à-dire le dos et le devant, le doyen déclarant et  
shown the double image of a man, that is to say the back and the front,  the dean declaring and

prétendant menteusement que c’était le véritable suaire dans lequel notre Sauveur Jésus-Christ avait 
claiming untruthfully that it was the true burial shroud in which our Saviour Jesus Christ had
 Ã©té enveloppé dans le tombeau, et sur lequel le portrait de Sauveur était resté imprimé avec les plaies 

been wrapped inside the tomb, on which the Saviour's portrait had been imprinted with the wounds 
qu’il portait.
that he bore.
 [...] En outre, pour attirer les foules afin de leur extorquer sournoisement de l’argent,    
In addition, to draw crowds for the purpose of extorting money slyly, 
 
 de prétendus miracles ont eu lieu, certains hommes étant loués afin de se donner pour guéris 
 so as to claim that miracles have occurred, using hired men as to make it appear they had 
  
 lors de l’exposition du suaire, dont chacun croit qu’il est le suaire de Notre-Seigneur. 
 been cured upon exposure of the shroud, each convinced it is the shroud of Our Lord.
Mgr Henri de  Poitiers  de pieuse mémoire, alors évêque de Troyes, étant mis au courant de ces faits
 Bishop Henri de Poitiers of pious renown, then bishop of Troyes, being made aware of these facts 
 et pressé d’agir par de nombreuses personnes prudentes, comme c’était en effet son devoir
 and urged to act by many responsible people, as was indeed his duty 

sa juridiction ordinaire, se mit à l’oeuvre pour découvrir la vérité dans cette affaire.
in the exercise of his ordinary jurisdiction, set to work to uncover the truth in this matter.

Car beaucoup de théologiens et de personnes visées déclaraient qu’il ne pouvait s’agir
 For many theologians and persons who were consulted (had) declared that it could not be

 du suaire authentique de Notre-Seigneur dont le portrait se serait ainsi imprimé dessus,
the authentic shroud of Our Lord whose likeness had been imprinted upon it, 

puisque les saints Evangiles faisaient pas mention d’une telle impression, alors que si elle s’était produite,
as holy Gospels did not mention such an impression, whereas if it had occurred,
 
il semblait bien évident que les saints évangélistes n’auraient pas omis de le rapporter,
it seemed obvious that the Evangelists would not have omitted to report it,
  En fin de compte, après avoir déployé une grande diligence dans son enquête et ses interrogatoires,
In the end, after a thorough investigation  and interrogation, 

et que le fait ne serait pas demeuré  caché jusqu’à nos jours.
and that the fact would not remained hidden until today.

il a découvert la fraude et comment ledit linge avait été astucieusement peint,
he discovered the fraud and how the said cloth had been cunningly painted,  

 la vérité étant attestée par l’artiste qui l’a peint, autrement dit que c’était une oeuvre due au talent d’un 
 the truth being attested by the artist who painted it, namely that it was the talented work of said
 
homme, et non point miraculeusement forgée ou octroyée par grâce divine»
man, and not miraculously wrought or bestowed by divine grace "
(Texte latin reproduit par U. Chevalier, Etude critique sur l’origine du Saint Suaire de Lirey-Chambéry-Turin, 1900, Annexe, document G, p. VII-VIII).

(Latin text reproduced by U. Chevalier, Critical study on the origin of the Shroud of Lirey-Chambéry-Turin, 1900 Annex G, p. VII-VIII).


xxxxxx   (expect a few carefully-chosen words to appear here later).

Then there's this passage from Barrie Schwortz's shroud.com site (history page). I'll quote it in full, so as not to deprive readers of essential context, but the crucial few words come right at the end (highlighted in red):

April 14, 1503 Good Friday: Exposition of the Shroud at Bourg-en-Bresse for Archduke Philip the Handsome, grand-master of Flanders, on his return from a journey to Spain. The Shroud, which has been specially brought from Chambéry, with great ceremony, by Duke Philibert of Savoy and Duchess Marguerite, is exposed on an altar in one of the great halls of the Duke's palace. Savoy courtier Antoine de Lalaing records of the events of that day: "The day of the great and holy Friday, the Passion was preached in Monsignor's chapel by his confessor, the duke and duchess attending. Then they went with great devotion to the market halls of the town, where a great number of people heard the Passion preached by a Cordeilier. After that three bishops showed to the public the Holy Shroud of Our Lord Jesus Christ, and after the service it was shown in Monsignor's chapel." Lalaing adds that the Shroud's authenticity has been confirmed by its having been tried by fire, boiled in oil, laundered many times 'but it was not possible to efface or remove the imprint and image.'


This blogger has previously  taken that  account with a pinch of salt. But he'd now reconsidering in the light of the new model, when a Mark 1 image may have been gradually fading from view some 150 years after manufacture, but a ghost Mark2 image was being seen to take its place. Is it not perhaps unsurprising that an attempt would be made to achieve uniformity by speeding the removal of the degraded Mark1 image, especially if cautious testing had determined that the Mark2 image, while faint, was a lot more permanent and resistant to removal?  Why would that be? This little experiment with bleach and a thermal scorch may give a clue:
Top half: thermal scorches untreated. Lower half: excised portions of same scorches after steeping in bleach for 1 hour.


Close-up view of above


Those thermal scorches are not totally resistant to the bleach, though some of the loss may be due to mechanical effects (breaking off due to swelling of fibres). Irrespective, it's clear that thermal scorches can at least partly resist a harsh chemical like bleach, when the same agent decolorises my pomegranate dye extracts within a few minutes at most. Is it a mistake to imagine that a chemical scorch producing the hypothesized Mark2 ghost image has a similar chemical make-up to the thermal one above, i.e. dehydrated and oxidized linen carbohydrates, and while fainter than the Mark1 image is essentially permanent, resisting atmospheric oxygen, moisture, acidic pollutants etc and thus still visible (just) after many centuries, despite fires and the alleged treatments described above by courtier Lalaing?


Next experiment?

Linen, pomegranate, gum arabic crystals and bas relief template
Watch this space.

OK, that didn't take too long. The imprinting medium was pomegranate extract, alum and gum arabic. The template was painted iron, with some interesting rust patches even after giving a coat of metal undercoat. A litle iron does not hurt in this ranging shot experiment (see title). The imprinting was done two ways, using methodology developed in my earlier heat scorch experiments: LUWU (Linen Underneath with Underlay) and LOTTO (Linen On Top with Overlay).

That's the template being removed in the LUWU configuration; the completed imprint on the right was performed using LOTTO (see above).

More later, but please remember: what you see above are only the primary Mark1 images. They are of no relevance to the present TS image if, as hypothesized, we are now seeing only the secondary Mark2 ghost images formed by slow chemical action of dye/mordant imprinting chemicals, e.g. alum, sulphuric acid, iron salts etc., the Mark 1 image having disappeared long ago.

This posting is long enough as it is: so don't be surprised to see a new posting in due course in which the above images are tone-reversed and 3D-rendered, simply to see how well they compare with the thermal scorches. They will then be put away for months, maybe years to monitor the effects of time.

Afterthought: there's a major problem still to be addressed with the new model - the 'reverse side'. Even with the viscosity aid recommended by Accetta (gum arabic) there was extensive reverse side imaging.

Reverse side Mark1 images. Yes, they might disappear with time, maybe decades, maybe centuries, but would they not leave Mark 2 images on that same reverse side, which are NOT a feature of the TS?

 Pigment/mordant on the reverse side should surely generate a reverse-side Mark 2 image in the fullness of time - as acknowledged at least nominally in the earlier graphic. Can the problem be resolved? Maybe. The linen used in this experiment was very thin compared with others used in this ongoing project. Maybe viscosity aids like gum arabic* are not sufficient. Maybe the interstices of the weave need to be plugged with a cement-like substance. But with what? Dare on suggest that there's a potential role here for Rogers' starch* - not as a technological weaving aid, but as aid to unilateral printing. Would that be raw starch, with intact discrete starch granules, or gelatinized starch, with dispersed starch?  Granted, adding starch to the formulation introduces yet another ingredient, another variable, another complication, and the inevitable references to Occam's razor. But there's a upside too - if there were a starch 'skin' on the linen first, then a second aspect of the TS image can be explained, namely Rogers' observation that the image layer can be stripped off, and is exceedingly thin (estimated at 200-600nm based on failure to see in cross-section under a light microscope). In this scenario, the Mark 1 image layer could be on a starch coating, or linen fibres or both, with mordant acting as a bridge between dye and binding substrate. Where would the Mark 2 image form?  Starch? Fibres? At least the model offers possibilities for testing these alternatives using adhesive tape, microscopy etc, essentially as deployed by Rogers and his STURP colleagues.

 It was the reverse side problem that persuaded this blogger against going down the soluble dye road, to say nothing of STURP's failure to link the body image with external pigments of any kind, and instead to focus on thermal scorching. The latter coudl be said to be 'on the back burner' while the strengths and weaknesses of the current dye/mordant model are investigated more thoroughly, especially when  assisted by starch, viscosity agents etc if able to prevent dye migration across the weave,

* Here's what Joseph Accetta  had to say re starch and gum arabic in his St.Louis paper (I've corrected his spelling of 'Rogers').


We could speculate that the starch likely present in the cloth reacted with the gallate ink rather then the cellulose itself. Gum Arabic which is a complex and variable mixture of arabinogalactan oligosaccharides, polysaccharides and glycoproteins and a common binder for coloring agents and may have been responsible for the effect observed by Rogers and Adler that the sepia coloring agent literally peeled off from the fiber leaving only the uncolored underlying fiber however no protein in the image areas was found . The initial protein may be bound chemically in ways not amenable to test . In summary, there is a relatively wide range of chemical reactions that that have not been investigated and further the colored fibrils should be subjected to all of the means of modern analytical techniques to specifically define the molecular composition of the coloring and this will require attendant access to the cloth for further sampling.