Thursday, April 9, 2015

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?

31 comments:

Adrie said...

Hello Colin,
Now you’re planning to do an experiment with nitric acid fumes, I felt I had to remind you that PMS found no “nitrogen-containing contaminants” on image fibers (Rogers, Scientific Method). Whether this might be explained by a bad signal-to-noise ratio and whether it is still worth risking your lungs for, is something you can decide, better than I do.
Thanks anyway for the experiments done recently. Take care.

sciencebod said...

Yes, we had this discussion a while ago, Adrie, when you reminded me of the "no extra nitrogen" claim. I seem to recall responding that was evidence against any hypothesis based on external nitrogen, including Rogers' putrefaction amines! So why was Rogers unconcerned?

I had in fact recalled that criticism you raised when formulating my new "fumigation" hypothesis. Here's my response: firstly the nitric acid might behave purely as an oxidising agent towards carbohydrates etc, creating conjugated double bonds etc, leaving no nitrogen residue in the cloth (when HNO3 oxidizes, gaseous NO and/or NO2 are formed as products so could escape).

The chief problem arises where the proposal for a xanthoproteic reaction is concerned, generating yellow chrompohores generating aromatic nitro-groups. But how was the nitrogen determined in those early studies? Was it a wet Kjeldahl assay for nitrogen in amino/amide/peptide linkage only, which I doubt. Instrumental? How? Might it have failed to pick up nitro- groups without prior reduction? It takes quite powerful reducing agents (dithionite etc) to reduce -NO2 to NH2.

Nice to hear from you, by the way. Incidentally I'd be interested to hear your views on whether infrared reflectance spectra of TS image fibres might allow for aromatic nitro groups, especially nitrotyrosine.

Adrie said...

Rogers, after mentioning the negative PMS result, only said that microchemical testing confirmed this:
“The pyrolysis-mass-spectrometry analyses of individual fibers at the NSF Center of Excellence at the University of Nebraska was sufficiently sensitive to detect ppb levels of polyethylene oligomers that came from sample bags, but it did not detect any of the possible pigments or painting media. The pyrolysis-MS analyses did not detect any nitrogen-containing contaminants. This seemed to rule out glair (egg white) as well as any significant microbiological deposits. These results were confirmed by microchemical testing.” https://www.shroud.com/pdfs/rogers2.pdf

Heller and Adler used
“a) diphenylamine b) fast blue salt B” for the detection of “nitro derivatives” and
“a) ninhydrin b) fluorescamine” for detecting “amines, primary” and more tests for other nitrogen-containing substances and got negative results from image fibers (A Chemical Investigation, 1981). Their table 7 listing all their tests for organic structures and functional test is online at p.54 of
http://books.google.co.uk/books?id=J2jBnDN3VxMC&printsec=frontcover&dq=orphaned+manuscript&hl=en&sa=X&ei=aq-tU72GKOqm0AWDw4DwBw&ved=0CCEQ6AEwAA#v=onepage&q=table%207&f=false

As for the FTIR results of nitrotyrosine, shown in your pop-up, http://colinb-sciencebuzz.blogspot.nl/2015/04/might-fumigation-with-nitric-acid.html , the peaks seem to be at ca. 1170 (large), 1270, 1330 (large), 1420, 1540, 1600 (small) and 1750 cm-1 (+- 10?). Of the four FTIRs of Shroud image fibers that I know of, all have a very characteristic peak at ca. 1600 cm-1 (not present in linen), but only two have a peak at 1170 and three have a peak at 1330 and four have one at 1420. These last three wavenumbers are also present in linen. A 1540 or 1750 peak is not found in any image FTIR and is not present in linen either. A very small 1270 peak might be present in one image FTIR, but is not present in linen. So, at first sight, the nitrotyrosine FTIR does not strike me as fitting the Shroud image. The ‘newest’ image FTIR is online in fig. 23 of this 2015 paper http://www.shs-conferences.org/articles/shsconf/pdf/2015/02/shsconf_atsi2014_00004.pdf

Hope this helps.

Adrie said...

By the way, I just now saw that I mistook your pop-up for a FTIR spectrum of nitrotyrosine, while in reality it is a IRDPM spectrum of nitrotyrosine. This might change a lot, I don’t know. I'm sorry.

Adrie said...

IRMPD of course.. I'd better take some rest..

sciencebod said...

Holding answer: it might seem to outsiders that I have hit the buffers, the predictably very substantial van der Hoeven buffers.

But I have news for you, Adrie. Sorry if I haven't mentioned it before. It's never been my aim to recreate the TS in every detail - how can I, not knowing who made it, when it was made, the source of materials and energy? Even if I thought I had an exact replica, what guarantee is there that the powers that be would allow me to examine the TS to check the correctness or otherwise of my ideas?

No, my objectives are more limited. They are to show how the TS image MIGHT have been created using medieval technology, as a counter to the agenda-driven pseudoscientists who maintain that science is stumped for answers, that if science cannot re-create the TS in every detail then ipso facto the TS is beyond the realms of science and serves as proof for the Resurrection of Jesus.

I have no problem whatsoever with the resurrection/re-visit to fellow disciples of Jesus, even if it's not essential to a belief in his ultimate divinity. What galls me are so-called scientists claiming that a 200nm thick image could ONLY have been generated by supernatural means, which is complete and utter codswallop, given that the superficial PCW of linen fibres also happens to be that thickness, give or take, AND has a composition different to the underlying SCW. There is nothing miraculous about 200nm thick layers if one takes the trouble to acquire a little botanical and chemical knowledge.

The arrogance of those (so-called) physicists takes one's breath away. In fact, they are not physicists. In the UK they would be called technologists. Technology, while partnered with science, is entirely different in its methods and aims needless to say, being concerned with the world of applications rather than ideas.

sciencebod said...

Good morning again Adrie. I was trying to follow up your reference to Adler having used a colorimetric tests for "nitro derivatives". Can you provide a link (but if it's that oddly-named pastiche of folksy papers under the title 'Orphaned Manuscript' then a particular one may or may not be accessible at my end under Google Books - having used up my page "ration" long ago).

I tried googling naturally. All that came up was your comment yesterday on this site (every cloud has a silver lining). But I did come across a fascinating point made in a 1924 paper (added as postscript) on gun cotton (nitrated cellulose) to the effect that the explosive "leaks" its nitrogen slowly as NOx. While aware of the difference between nitrate esters (cellulose nitrates) and true nitro compounds (with direct C-N links), both of which can decompose explosively at least when heavily nitrated, it's not impossible that nitrotyrosine etc that formed centuries ago may have gradually shed its nitrogen (assisted by the 1532 fire?).

Come to think of it, was it really a drop of molten silver that did so much damage? Silver was never detected, and its MPt. looks too high for the "silver" reliquary to have melted. Might it have been a localised area of explosive -NO2 decomposition within the chemcically-modified fibres of the TS wotdunnit? Is the present TS in its glass case a ticking time bomb? Just a thought. I'll be back later with some hopefully more sober comment!

Adrie said...

Goodmorning Colin. I’ll scan the whole 1981 article of Heller and Adler and mail it to you. The diphenylamide test has a reference to Fiegl, F., and Anger, V., Spot Tests in Organic Chemistry, 7th edition, translated by R. Oesper, Elsevier Publishing Company, Amsterdam, Netherlands, 1966.
That nitrogen can leak out of nitrated cellulose is indeed interesting.

sciencebod said...

Thanks Adrie. I'll look forward to reading (or re-reading) the full paper. I may have seen all of it in dribs and drabs these last 3 years on different laptops via Google books, but never all at the one sitting, thanks to page "rationing". Given what I read about bilirubin ("extraordinary amounts" based on non-definitive spot-tests) was not authoritative, and indeed inflicted pseudo-science on the chemically less-informed, assisted by Barrie Schwortz's personal anecdotes, I have been unwilling to part with good money to see the "Orphaned Manuscript" in its entirety. BS of course holds the copyright on Adler RIP's writings. Nuff said.

Incidentally, are you quite certain that Adler's diphenylamine reagent works for aromatic nitro-compounds (nitrotyrosine etc)? I've so far only been able to find a reference to it working for aliphatic nitrocompounds (e.g. nitromethane etc.

http://nvlpubs.nist.gov/nistpubs/jres/049/jresv49n3p163_A1b.pdf

While the paper does not specifically exclude aromatic nitro-compounds, I see that one of them ("nitrostyrene"), presumably token, was tested but gave a negative response.

Adrie said...

Google books has a more modern Fiegl and Anger, and it says that diphenylamine detects p-nitrosophenol (p. 363). I’ll send the screenshots to you. I don’t know whether or not this is a too simple equivalent to nitrotyrosine, but at least it is an aromatic nitro-compound.

https://books.google.nl/books?id=6pqEiUhHsmgC&pg=PA4&dq=Fiegl,+F.,+Anger,+V.,+Spot+Tests+in+Organic+Chemistry,&hl=nl&sa=X&ei=B_EoVfvkMsj1avXqgeAK&redir_esc=y#v=onepage&q=diphenylamine&f=false

sciencebod said...

Nitroso- compounds are entirely different, Adrie, being chemically far more reactive than nitro-derivatives. The nitrogen is in a lower oxidation state.

I can find no evidence (as yet) that the other Adler reagent you mention - Fast Blue Salt B- works for nitro-derivatives as suggested, whether aliphatic or aromatic. The chloride salt contains a positively charged diazonium ion in salt form, not dissimilar from the 'diazo reagent' used to test for phenols and bilirubin (Ehrlich reagent. Indeed it's been recommended as a spot test for bilirubin (but still non-conclusive!).

Here's how it's described one one site I've jest visited:

"Fast Blue B reagent [tetraazotized di-o-anisidine] for detection of cannabinoids, phenols, tanning agents, amines which can be coupled"

No mention there of nitro-compounds. Nitro substituents withdraw electrons from aromatic rings making them less reactive. Anyone who's tried converting nitrobenzene to di- or tri-nitrobenzene as I have will know what I mean.

I'd like to know why Adler mentioned "nitro-derivatives" specifically in connection with those two spot tests. On what grounds might he have suspected their presence on Shroud fibres?


Adrie said...

Feigl and Anger say that Fast Blue Salt B detects primary aliphatic nitro-compounds, but that secondary nitroparaffins and aromatic nitro compounds do not react (p. 296). I’ll send the scan again.
Why Heller and Adler looked for nitro-derivatives I don’t know. All I know is that a Corona discharge seems to produce ozone and nitric acid

(http://www.ohioshroudconference.com/papers/p15.pdf p. 5).

https://books.google.nl/books?id=6pqEiUhHsmgC&pg=PA4&dq=Fiegl,+F.,+Anger,+V.,+Spot+Tests+in+Organic+Chemistry,&hl=nl&sa=X&ei=B_EoVfvkMsj1avXqgeAK&redir_esc=y#v=snippet&q=Fast%20Blue%20Salt%20B&f=false

Adrie said...

Just now I also found that diphenylamine detects some aromatic nitro compounds. Feigl and Anger p. 295 says “It revealed … nitrobenzene … dinitrobenzene … nitroaniline … nitrophenol … nitronaphtalene … etc. I’ll send the screenshot.

https://books.google.nl/books?id=6pqEiUhHsmgC&pg=PA4&dq=Fiegl,+F.,+Anger,+V.,+Spot+Tests+in+Organic+Chemistry,&hl=nl&sa=X&ei=B_EoVfvkMsj1avXqgeAK&redir_esc=y#v=snippet&q=Fast%20Blue%20Salt%20B&f=false

sciencebod said...

Yes, that fast blue salt reacts with aliphatic nitro compounds only. It's to do with the tautomeric "aci" forms that are possible through having hydrogen attached to the N-linked carbon atom. The hydrogen migrates over to the nitro oxygen, and in alkali a negative ion then forms:

https://books.google.co.uk/books?id=25H-BAAAQBAJ&pg=PA331&lpg=PA331&dq=nitroalkanes+aci+form&source=bl&ots=GGhIGG9wwv&sig=l7t_eyVVSJv78AjOo2CFTSYFAk4&hl=en&sa=X&ei=VCEpVbyQJYKP7AaduYCQBw&ved=0CC0Q6AEwAg#v=onepage&q=nitroalkanes%20aci%20form&f=false

None of that essential tautomerism is possible with aromatic nitro compounds, in which the N-linked aromatic ring carbon carries no hydrogen, being bonded to two other carbon atoms.

Adrie said...

Yes, I see what you mean.

sciencebod said...

"Just now I also found that diphenylamine detects some aromatic nitro compounds."

Yes, that's a separate variant of the test that requires a raised temperature to physically melt the diphenylamine. Would Adler have gone to that trouble I wonder if simply screening for a wide range of functional groups (Table 7)? Would he have felt it essential to dot all the i's and cross all the t's? I doubt it somehow, unless like me he had a particular reason for suspecting the presence of nitro groups, or a particular reason for needing to exclude them..

Adrie said...

Well, of course I don’t know for sure, but Heller and Adler do mention the a) diphenylamine and b) fast blue salt B test in their table 7 and refer to pages a) 295 and b) 296 of Feigl and Anger for these respective tests. On these same pagenumbers the online Feigl and Anger describe exactly only the heated diphenylamine test, and not another diphenylamine test(p. 295), and the fast blue salt test (p. 296). This can hardly be a coincidence..

I see now, that, in fact, the online version I quoted is not another edition but simply the seventh impression, 2001, of the seventh English edition, 1966, by Elsevier, Amsterdam (pagina iv), the one that Adler refers to. It’s a coincidence that I picked this one from Google books..

I'll send the screenshot.

https://books.google.nl/books?id=6pqEiUhHsmgC&pg=PA4&dq=Fiegl,+F.,+Anger,+V.,+Spot+Tests+in+Organic+Chemistry,&hl=nl&sa=X&ei=B_EoVfvkMsj1avXqgeAK&redir_esc=y#v=onepage&q=Elsevier%20Science&f=false

sciencebod said...

I tried Ref 42 on Table 7, Adrie. Being a pdf it was not a live URL, and not even cut-and-paste friendly. As for refs to 242/246, they weren't there at all. Full credit to you for following up, and concluding, quite reasonably and probably correctly, that the fused phenylalanine test WAS performed.

Maybe the fumigation model is a dead end, and maybe I'll have to discard it, as I've discarded so many other possibilities. But it will take more than a list of spot tests performed on sticky tape samples, probably with tiny amounts of material, to make me shelve the current project. There's an awful lot that can be explained, even assuming that those fumes worked via accelerated oxidation only (nitration to produce yellow xanthoproteic products is a bonus).

Still no nitric acid, and the supplier says that while it's dispatched, I may have to wait till Wednesday 22nd for it to arrive. I'll just have to be patient. I've already imprinted linen with gelatin. If forced to wait longer, I'll imprint with starch, flour etc so that when the acid arrives there can be some quick feasibility tests, results of which will be reported here immediately (with photographs).

What a pity that STURP did not think to document the results of all its tests, those somewhat subjective colorimetric and other micro-spotting ones especially, WITH PHOTOGRAPHS, given the time-constrained and (possibly) one-off nature of their access to the real thing.

Thanks for your interest and work in keeping me supplied with pertinent literature.

What's you model for image-imprinting, Adrie? I'm genuinely interested in knowing.

sciencebod said...

Typo: diphenylamine test.

Adrie said...

Hello again Colin.
I guess it’s not hard to guess what my model would be: that a coating of acid starch paste plus acid madder dye got oxidized by one or more of the side effects of a Corona discharge (heat, UV luminescence, ozone, nitric acid and other reactive substances). So it’s not much different from yours, at molecular level.

sciencebod said...

Yes, but you've left out a vital part, Adrie: the mechanism of image capture. If your model requires radiation, it would have to be (a) brought to a focus with a lens or pinhole (b)collimated, presumably with air attenuation in order to capture depth information for 3D properties (c)of the correct frequency to produce heating and/or chemical change in carbohydrates, without simultaneous scorching of hair (keratin protein).

Reminder: my model (and that Of Luigi Garlaschelli's) needs no radiation - simply manual moulding of linen to a 'painted' human subject or an effigy thereof.

If the mechanism were miraculous, so as to send modern man a message that all is not explainable by science, then why the 'wrong' radiocarbon date? Why make the image 200nm thick or greater - the thickness of the PCW. Why not make it 50nm thick or less? That would really give Paolo Di Lazzaro something even less explicable to bang on about than a plain old coloration of the entire PCW.

Adrie said...

Well, I can’t answer the why questions. I can say that a Corona discharge is not a simple radiation, in the sense that it has to be brought to focus, collimated and attenuated artificially. Experiments by Fanti and others showed that a CD does all this automatically to some extent as a result of the shape of the electric field. It also can ‘imprint’ an image of salty or oily hair on linen (Fanti 2005 fig. 12). What happened to the hair I don’t know, but the madder dyestuffs alizarin and purpurin, being easily oxidizable substrates, would probably get oxidized before the hair was burnt.

Fanti et al 2005: http://www.dii.unipd.it/-giulio.fanti/research/Sindone/corona.pdf

Adrie said...

It seems the hair was imprinted on photographic paper, by the way. It's not completely clear from the text.

sciencebod said...

OK, it's a corona discharge you say Adrie? That as you say is not em radiation - it's ionized air molecules - with a surplus or deficit of electrons.

I looked into that and Fanti's experiments a while ago, and seem to recall thinking there were some serious shortcomings in the model, but can't recall all the reasons off the top of my head.

I'll let you know if it all starts coming back to me, but that might take a little time - days rather than hours.

sciencebod said...

Did you see the two pictures I added to the end of the posting Adrie? They offer no comfort or support for Fanti's corona discharge theory - and indeed could be said to fatally undermine it.

Hair (or rather its behaviour) is always the give-away for separation of +ve and -ve electric charge between body and surroundings, or even buildup of a surplus of one kind of electric charge on the body.

The first of those is modelled by rubbing a balloon (for convenience) or pretty well anything against cloth and bringing close to the head. It doesn't matter which kind of charge, +ve or -ve, is present in excess on the balloon. It induces an opposite charge on the hair, resulting in the light hair being attracted to the balloon. In common parlance, the hair can be made to stand on end.

The second model is to charge up a Van De Graaff generator and place one's hand on the sphere (favourite school physics demo). Again, the hair stands on end. This time the surplus of charge is on the body itself, including individual strands of hair. The latter, being light, are then mutually repelled. The hair has again acted as a 'reporter' for charge imbalance.

Now consider the TS image. There is no evidence of the hair standing on end. Indeed - it is precisely the opposite. Many have commented that it seems to hang down too straight as if rigid. One could envisage it being attracted to the skull, but how could that ever happen in a corona discharge model? How could the hair come to have an opposite charge from the rest of the body, including the head.

Moisture, even moist air, is of course the enemy of all these static electricity experiments, but given the sizeable time lapse between deposition from a cross and image-imprinting in most models in which the TS is referred to as a burial shroud, bodily moisture had plenty of time to evaporate.

My model actually assumes body moisture, lots of it in fact as perspiration, the body image being a simulated sweat imprint left by a body on J of A's linen used to transport from cross to tomb, and probably NOT intended as the final burial shroud, that being used after washing to remove blood etc.

Adrie said...

Hello Colin,

The electrostaticity of hair and the TS hair position has been discussed by Fanti in his articles, of which I gave the URLs above. Now, I hope they are links:

Fanti et al. 2005 (p. 3)

Fanti 2008 (p. 18-19)

sciencebod said...

OK. I'll take a look when I have a free moment, Adrie. But I frankly do not have a lot of time for wacky models that attempt to bridge a gap between science and the supernatural. If it attempts to bridge that gap, it ain't science.

John Terry said...
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John Terry said...
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