Home > Science > In the Weeds: Vanillin and the Age of the Shroud

In the Weeds: Vanillin and the Age of the Shroud

July 20, 2015

Is there any validity believing that a lack of vanillin says anything about the shroud’s age?

imageTopic drift is a fact of life in this blog and almost every blog I’ve encountered. It is not a problem; it’s a useful feature. We were talking about radiation models for the images on the shroud and the subject of vanillin came up; it’s not important why. This caused Colin Berry to respond in the weeds – that is over in his blog – with an unrelated update to a posting on a different subject. Anyway that is how we got to this yesterday:

Vanillin is not a separate component from lignin. In fact it’s not even a component of  flax or linen. It’s a degradation product of lignin, derived from oxidation, side-chain shortening (loss of 2 carbons)  and detachment starting with one particular  monomer in the complex resinous polyphenol that is lignin, ie. coniferaldehye. See my earlier posting on the subject, this site.

Ray Rogers no less described and discussed vanillin as though it were a preformed component of lignin that gradually reduced with age. Nope: as the lignin oxidizes, the vanillin is newly formed, and being a relatively small molecule, gradually evaporates away, being responsible for the distinctive aroma of old lignin (the ability to detect it by smell being a sure sign that molecules are escaping into the air).

Anyway, if you haven’t read [Colin’s] earlier posting on the subject, you should. Do we really understand if the vanillin claim is valid?

And if you want to know what in the weeds means, it is this: In golf, when a shot lands on the fairway, it’s in plain sight in easy-to-play short grass. When a shot lands to the side, it’s in unkempt grass, and the golfer wastes time trying to find the lost ball. He’s literally "in the weeds".  And Colin wants to know why Google and people don’t find what he writes about on his blog.  There is a practical limit to topic drift.  What does comments about vanillin have to do with Here’s an updated version of my ‘iconoplastic’ modelling of that Turin so-called “Shroud” (probably a misnomer)?

Anyway, NOW, the topic is vanillin and the question is this: Is there any validity believing that a lack of vanillin says anything about the shroud’s age?

“Tell me this,” Colin writes:

What is the use of a clock that is either running, or has stopped completely? That is the situation with the Shroud linen. We are asked to believe that it’s the absence of Wiesner-reactive lignin that is the reason, ie that it is incredibly aged.

Sorry, I don’t buy that. The “vanillin clock” is so poorly documented that I decline to believe that the absence of a positive test is necessarily to do with age. It could be due to any number of factors….

And Colin gives us an alternate possibility, the sort of thing lawyers like to do to make us have reasonable doubts about a defendant in a criminal trial:

… someone decided to fumigate the reliquary (see my earlier comment). They removed the TS, then inserted a lit sulphur candle. Later the candle was removed, and the TS replaced, with its long sides folded in towards the middle before folding or rolling. Residual SO2 made better contact with the central regions of the TS than with the edges. So the reactive aldehyde groups of lignin in the initially peripheral Raes threads were better protected from the SO2 than the more central threads.

I’m not suggesting this was the actual process that gave the difference between Raes v the rest, but it’s an indication of the uncertainties that attach to using a chemical as distinct from radioactive clock, where one is at the mercy of environmental conditions that one can only guess at, as I am guessing right now.

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  1. daveb of wellington nz
    July 20, 2015 at 5:32 am

    ” … as the lignin oxidizes, the vanillin is newly formed, and being a relatively small molecule, gradually evaporates away, being responsible for the distinctive aroma of old lignin (the ability to detect it by smell being a sure sign that molecules are escaping into the air).”

    I can do Topic drift too: Early in my career, I used to work with several gangs of bridge carpenters (some of our old bridges were still built in timber). They could pick up a chip of wood lying around, smell it, identify it, and give their verdict: ironbark, turpentine, totara, kahikatea, or whatever it might be, and they’d always be right. Of course flax isn’t timber, and they were probably picking up the smell of the residual gums and resins. Wouldn’t know if they could pick up vanillin, but some of our old Maori kuia used to weaving flax probably would.

  2. July 20, 2015 at 5:51 am

    Yes, Dan, but it’s not because I’m adding new material unrelated to the blog title that is the problem where the increasingly law-unto-itself Google is concerned. One can enter the entire title of my latest posting into Google, and it will have a blind spot for my posting. Why? The answer is clear: it considers I have misspelt my neologism ‘iconoplstic’ believing i really meant to say ‘iconoclastic’ despite enclosing it inverted commas. It then proceeds to list returns with ‘iconoclastic’ scored out after each entry, i.e. apologizing so to speak for failing to find links that include ITS key word, not mine. This is bizarre and dare one say arrogant behaviour on the part of Google. As recent as yesterday it was failing to “find” my posting, but picking up secondary mentions, as the one on this site. Today, it’s finally found it, but displayed it against my name first instead of more user-friendly title.

    None of this nonsense happens when I post to my sciencebuzz site. Why is that? That has Google-owned Blogger Blogspot as host, and I suspect it’s one rule for those in the Google stable, a friendlier more ‘forgiving’ rule, and a different one for those on WordPress, present company excepted where other factors outweigh the second-class citizen treatment.

    The EU is currently taking a long hard look at Google’s abuse of its (constructive) monopoly, and not before time. Google needs a good hard kick up its derriere.

  3. Hugh Farey
    July 20, 2015 at 6:05 am

    I think the point about the vanillin is not how much there is in absolute terms, but the fact that Rogers claimed a difference in vanillin between his Raes fibres and his ‘main body’ fibres. If the two were really from different ages and provenance, then the difference could be significant. Unfortunately, as with most of Rogers’s later papers, it is not clear whether all his fibres were what he thought they were, or whether the same test was applied to the two differently sourced samples or what his comparison samples were, or how they were tested.

    • Nabber
      July 20, 2015 at 4:08 pm

      Always use the instant “sniff test” on this website: Hmmmm…. Rogers or Berry, Rogers or Berry, “geez, no contest”. Nuff said. (For the weak of mind: It’s “Rogers” every time).

  4. piero
    July 20, 2015 at 11:49 am

    I have seen that Colin wrote “Pomer”
    instead of “Pomar”:

    >Note especially the listings for authoritative Pomer paper
    (first and second).
    The latter states “it is unlikely that vanillin contributes
    to a great extent”.

    Link:
    https://shroudofturinwithoutallthehype.wordpress.com/2014/01/31/critique-of-rogers-so-called-vanillin-clock-for-dating-the-shroud-why-was-stanley-t-kosiewicz-not-a-co-author-and-wheres-the-data/
    — —
    In the past I wrote (in an Italian blog)
    some line about:
    Wiesner test, Patrick Berger, Pomar and Shroud:

    >Nel titolo dello studio di Pomar, Merino e Barcelo :
    “O-4-linked conyferyl and sinapyl aldehydes in ligniying cell walls are the main target of the Wiesner (phloroglucinol-HCl) reaction” vi è forse una traccia utile per i nostri dibattiti ?
    >In ogni caso mi pare che Berger non abbia dato un colpo decisivo alle questioni evidenziate dal chimico USA Rogers… Che ne pensate ?
    >La “competenza microchimica di Rogers” meritava forse qualche interessante pagina di commento nel libro di Baima Bollone (piuttosto che i “libracci” di Knight & Lomas e Picknett & Price, ecc. …)…

    Here a rough translation:
    >In the title of the study of Pomar, Merino and Barcelo:
    “O-4-linked conyferyl sinapyl and aldehydes in ligniying cell walls are the main target of the Wiesner (phloroglucinol-HCl) reaction” there is perhaps a trace useful for our debates?
    >In any case it seems to me that Berger did not give a decisive blow to the issues highlighted by the US chemical Rogers … What do you think?
    >The “microchemical competence of Rogers” maybe deserved
    some interesting page of comment in the book of BaimaBollone
    (rather than the “bad books” Knight & Lomas and Picknett & Price, etc. …)…

    Link:
    http://www.sindone.altervista.org/forum/viewtopic.php?t=59
    — —
    In my opinion you can use several techniques in order
    to test what happens during the Wiesner test:
    ATR-FTIR, AFM, CFM, AFM-Raman, SNOM…

    I think that ATR-FTIR can be interesting way.
    Do you agree?

    For example, I have found a paper titled:
    “Rapid semi-quantitative determination of aspen lignin
    in lignocellulosic products”
    by
    Urve Kallavus, Kristi Kärner, Kärt Kärner*, and Matti Elomaa

    Where ATR-FTIR was successfully used as
    method for the determination of aspen lignin…
    “…For the quantification of lignin content, a series of aspen
    wood powder/microcrystalline cellulose binder were mixed
    and analysed with FTIR-ATR and UV-VIS…”

    …Weisner and Mäule colour tests were used for staining
    to detect lignin in samples…

    Link:
    http://www.kirj.ee/public/proceedings_pdf/2015/issue_1S/Proc-2015-1S-105-112.pdf

    Unfortunately this work (to detect lignin in samples…)
    is a bit far from our own problem: the Vanillin test on linen fibrils…

  5. anoxie
    July 21, 2015 at 12:45 pm

    “And Colin gives us an alternate possibility”

    Actually it was an unconvinging answer to a question from Thibault Heimburger, who noted that Rogers used the Holland cloth as a control.

    “What if” the control was skewed by fumigation “so the reactive aldehyde groups of lignin in the initially peripheral Raes threads were better protected from the SO2 than the more central threads.”

    That’s pretty accurately agenda-driven SO2.

  6. piero
    July 22, 2015 at 10:33 am

    The method of “radioactive clock” (14C test) was used
    to test the Shroud only in an angle ….
    This cannot be the right way to solve the entire Enigma.

    The Vanillin loss from Lignin was an interesting way,
    but we cannot too trust in that particular test (in any case
    you still have to answer about my ATR-FTIR [or AFM,
    AFM-Raman, etc.] proposal to investigate the issue…).
    Instead a possible nano-sampling (perhaps you don’t believe
    too in the utility of the previous material: linen fibrils already
    taken apart from the Holy Shroud in the past and kept in a
    safe place… and then [in this case] you can integrate these
    old “macro-samples” with new nano-samples…) and a proper
    mapping [= nano-mappings] can contribute to solve the problem,
    obviously (IMHO) this will happen using advanced microscopies …

    Have you found other useful ideas?

    I underlined that ATR-FTIR was successfully used in the case
    of a ” Rapid semi-quantitative determination” of lignin… and I was
    curious to see your reaction in order to discuss around
    the Age of the Shroud and the ATR-FTIR [a technique already
    used by G. Fanti] …and then we have not yet further investigate
    the comparison for ATR-FTIR and AFM-Raman, etc. …with possible details…

  1. July 21, 2015 at 12:13 am
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