Home > Carbon 14 Dating > The Chemist Rogers and Plastic Bags

The Chemist Rogers and Plastic Bags

September 14, 2015

clip_image001Following the recent publication, There is no mass spectrometry evidence that the C14 sample from the Shroud of Turin comes from a “medieval invisible mending”  in Thermochimica Acta, co-author Marco Bella posted Sindone, il chimico, la fede e la scienza in the blog space of Il Fatto Quotidiano. It is in Italian. Fortunately, Marco has provided an English version as a PDF file.  It’s called, The Shroud of Turin, the chemist, the Faith and the Science.  It wraps up this way:

Therefore, it appears that Rogers was aware about the presence of a contaminant which would give a mass spectra quite similar (identical?) to the one actually observed for his mass spectra of Raes sample. Despite that, he did not mention these foreign peaks due to the contamination in his discussion of the spectra. There is no need to explain that plastic bags were not widely used around the Middle Age, and that if there are peaks coming from that material in a spectra these can only be due to modern contamination.

Mass spectrometry is widely used today in the identification of pharmaceuticals, drugs, food additives, toxins. Ironically, even the C14 analysis is based on mass spectrometry. What would happen if we started to interpret mass spectra in a completely wrong manner, e.g. in the similar way as in the Rogers paper? Here there are some examples: a drug dealer could not be condemned, food contaminated with high level of pesticides could be sold, an athlete putting his health at risk with doping could not be stopped, a lot of medicine with a toxic impurity could be given to patients.

There is no ‘innocuous pseudoscience”. Any pseudoscience is damaging, since it alters the perception of the real world and it is deeply non-educative. It might cause serious consequences, especially when health issue are involved. To believe in the pseudoscience of the Shroud has nothing to do with Faith, and especially believers should get offended versus people exploiting either their Faith or the human weakness of the chemist Rogers.

You will want to read this and think about it.

Categories: Carbon 14 Dating
  1. September 14, 2015 at 3:15 am

    The scope of manipulations by Bella and colleagues is horrific.

    I think someone has to deal with it.

  2. Tristan Casabianca
    September 14, 2015 at 4:44 am

    According to Bella, “Of course, no one was able to criticize the key findings of [their] work” on this blog!!!

    His definition of “pseudoscience” shows clearly that, unfortunately, you don’t need to understand philosophy of science to become a chemist.

  3. September 14, 2015 at 9:53 am

    Interesting new colour scheme Dan. Might it have been inspired by the notion of a lightly-toasted flour imprint?

    • September 14, 2015 at 10:36 am

      Or perhaps it’s a tea stain. Hmmmm.

      • September 14, 2015 at 11:19 am

        Tea stain? TS? Now why didn’t I think of that?

        Actually, tea stains are due to tannins, DavidG. Oh so last year… Some of us have moved on from purely chemical (or, before that, thermal, “scorch” imaging).

        Think thermochemical, and no, not hot tea….But don’t forget to wash out the Maillard-reaction crust, and then focus on what’s left – the far more subtle image underneath, probably confined to the interior of linen fibres.

        Plain white flour is far more versatile in terms of its thermochemical and image-imprinting capabilities. It provides protein, reducing sugars, oils etc.

        Flour does the business, being a thermochemical reaction cocktail, acting not only ON the surface of linen fibes, in response to applied heat, as in a medieval oven,
        but INSIDE them too…

    • piero
      September 14, 2015 at 11:35 am

      I believe that I’ll not be happy (I say this only speaking
      for hypothesis…) if someone will want to ask a
      quantitative assessment of the lignin content
      on linen fibrils (of the Holy Shroud) using mass spectometry…

      I say that because Dr. Ray Rogers indicated
      a quantitative evaluation of Lignin in his paper
      (= “Scientific Methods Applied to the Shroud of Turin.
      A review.”) and also he stated that differences between
      amount of lignin on linen fibers in the Raes sample
      and on Shroud samples are significant.

      Rogers indicated us that simple microscopic viewing
      was not sufficient to prove differences among the linen samples.
      In any case he indicated us that no samples of the
      Holland cloth or Raes threads had heavy deposits of lignin…
      Lignin amounts vary among Shroud locations and
      this can be an interesting fact when it’s correlated with
      the observations of bands of different colors…
      Newer linens are homogeneous and they do not show
      bands of different-colored yarn in the weave. …
      So…
      Colin,
      What is your opinion about the inherent implications
      What you can say to us about this fact?
      Have you an useful idea how to try to repeat
      your experiments using a substrate made (weaved)
      with different hank of linen yarns ? (…and at same
      time working with your model…)

      Link:
      https://www.shroud.com/pdfs/rogers2.pdf
      -*-*-*-*-*-*-*-
      Here another very little thing:
      “adhesive tape composition” (…and mass spectroscopy).

      Colin,
      What is your evaluation for possible solubility
      of the adhesive (= part of the tape) in the solvent (Xylene) used?

      Composition for the adhesive = an epoxy resin ???

      Unfortunately I have no past experiences in the field of
      application of “isotope ratio mass spectrometry” for
      discrimination and comparison of adhesive tapes…

      • piero
        September 14, 2015 at 11:38 am

        But …
        Here I want to better clarify the presumed problem:
        “adhesives” in adhesive tapes …!

  4. piero
    September 14, 2015 at 10:44 am

    If I am not mistaken, the abundances are not in the same proportions.
    For example: see the comparison for the peak 69 in Fig. The “preview”
    of Bella-Garlaschelli-Samperi and the same peak in the other Fig. 2
    (in the same “TCA preview” Bella-Garlaschelli).

    Y-axis and relative abundance:
    >…Signal intensity may be dependent on many factors,
    especially the nature of the molecules being analyzed
    and how they ionize.
    >The efficiency of ionization varies from molecule to
    molecule and from ion source to ion source. …
    (Link: https://en.wikipedia.org/wiki/Mass_spectrum )

    Bella wrote:
    >…It happens that “oligomers from polyethylene” show
    a spectra which peaks differ by 14 atomic mass units.
    >The parks at M=96 it is not furfural, but just one of these peak.
    >Therefore, the two spectra in Rogers paper differ only by
    the peaks of the contaminant.
    >I believe it is not necessary to explain that plastic bags
    were not so common in the Middle Age … etc. … etc. …

    Unfortunately, until now,
    I have not found the useful spectra (mass spectroscopy)
    and (also) Bella has not yet answered to me (on “polyethylene
    olygomers” …or … on solvated “tape adhesive” or
    fatty acid [coming from the people who were holding
    the Shroud during exhibitions/ostensions]???)
    using proper diagrams for inherent comparisons…

    So I should only indicate the famous proposition n. 7
    of Tractatus Logico-Philosophicus, by Wittgenstein:
    “Whereof one cannot speak, thereof one must be silent.”
    („Wovon man nicht sprechen kann, darüber muss man schweigen.”)…
    — — —
    Yesterday afternoon I have followed the lecture
    on “crop circles” by Paolo Attivissimo (an italian journalist).
    After depicting the history of crop circles
    (see also: the past interesting role played
    by Dough Bower and Dave Chorley…),
    he claimed to have participated
    (during this year 2015) in a construction of
    a big crop circle near Turin…
    This in the context of a three-day outline for the
    presentation of the museum “Falseum”
    (http://www.falseum.it/it/) which I have not visited
    because I had no more time …

    Here some particular conjectures:
    Was Raymond Rogers an absent-minded person
    (because he was a suffering person, with his cancer),
    a liar, a trickster or (perhaps) a sort of “circlemaker” ?

    • September 14, 2015 at 12:31 pm

      The clue to understanding why Ray Rogers, an acknowledged expert in chemical explosives, more specifically their stability and safety on storage, is to be found in John Heller’s book on Page 6
      .
      There he writes “Because of his work on explosives, Ray Rogers was an eminent expert in thermal effects”.

      No, he wasn’t an expert in thermal effects generally, in the sense of understanding or being able to predict the complex sequence of chemical changes that can be initiated by heat (that being a vast area in which no one individual can hope to know it all).

      There seems to have been a misunderstanding on the part of John Heller, and probably the initiators of STURP generally.

      Ray Rogers chose DSC (differential scanning calorimetry) as a means of monitoring the kinetic stability of chemical explosives. It involved applying metered amounts of thermal energy (“heat”) and monitoring temperature change. Flat regions on the heat/temperature plot are referred to as “endotherms” which indicate where heat is being absorbed to break chemical bonds, the first step in chemical reaction, and in this instance explosive decomposition,.Those endotherms can be used to calculate kinetic parameters (notably activation energy) but it’s arguably more physics (or physical chemistry) than test-tube chemistry.

      An expertise in DSC does NOT make one an expert in thermal breakdown pathways generally. It provides no data on detailed mechanism generally.

      Ray Rogers was pre-eminent in his field of explosives-stability testing. That expertise did NOT equip him to elucidate the mechanism by which the TS image was formed, whether thermal, chemical, or thermochemical. His elevation to role of chemical sainthood is sadly laughable to anyone with the briefest acquaintance with chemical science. That much becomes clear when one looks at the way his Pliny-era “starch-coating impurity” hypothesis is casually inserted into a pro-authenticity narrative as if fact, with the terms starch, impure starch, crude starch, starch fractions, dextrins, reducing sugars being used interchangeably.

      Starch is starch. It does NOT spontaneously break down to dextrins and reducing sugars on ageing. The Rogers “starch impurity coating” may be correct, but the “sugar-coated” extension of that hypothesis is/was palpable nonsense.

      Rogers was a gifted hands-on chemist, but he became increasingly prone to mix speculation and fact post the STURP 1981 Summary, as did other ‘leading lights’.

      Group think? Maybe. Group-think is the bane of science.

      • piero
        September 15, 2015 at 9:34 am

        Colin,
        your particular “chemical-sociological analysis”
        seems to be interesting (link: https://it.wikipedia.org/wiki/Groupthink and then see also: https://en.wikipedia.org/wiki/Deindividuation). But not decisive as regards the solution of the problem of mass spectroscopy on alleged “oligomers of polyethylene” …
        The point to clarify seems to be
        the determination about the chemical chain:
        “…a long chain aliphatic” ??
        (Is really the only key to solve the question?)
        But … How long is this -CH2- chain?
        Here I speak about the idea to measure the lenght of that methylene chain (-CH2-) starting from the key-number 14 (=12+2= one Carbon and two Hydrogen atoms)…

        Other questions:
        – Please, observe the peak 69 in “Shroud-image fiber”, this peak seems not to have the same higher (see also: “Y-axis and relative abundance”) in “Raes sample-fiber”…
        – The higher of the peak 131 is not the same (because it’s more high in “Shroud-image fiber”).
        – In the mass spectrometric diagram of “Shroud-image fiber”
        are present the peaks: 119(?),126(?), 169, 181 and 219. Instead there are not these peaks in the mass spectrometric diagram of “Raes sample-fiber”…

        So I think that a computer analysis of mass spectrometries (or the trained eye of an expert “mass spectroscopy analyst”) would save us time in order to solve the “little enigma”…

        • piero
          September 15, 2015 at 10:11 am

          Here some words, trying to return to the particular “chemical-sociological analysis” unveiled by Colin…

          I should be happy if the same relentless pursuit of “analytical perfection” (= regarding “polyethylene oligomers” or not …) would be happen about the ATR FTIR analysis. “The penetration depth into the sample is typically between 0.5 and 2 micrometres” (and this is the same [vague] information we can read in the book by Prof. Fanti).
          What can see into the linen fibrils using the ATR FTIR analysis?

          For example : in the book (by Prof. Fanti, it. edition pp. 294-295) there are two example of linen fiber diameter = 15.7 micrometres and 22.8 micrometres.

          So, we can try to calculate something…
          If you take the minimum penetration the percentage is the following:
          0.5/15.7 = 0.0318 = 3.18% —> 6.36% with respect the entire diameter
          05./22.8 = 0.0219 = 2.19% —> 4.38% with respect the entire diameter

          Instead if you take into account the maximum penetration the percentage is the following:
          2/15.7 = 0.12738 = 12.74% —-> 25.48% with respect the entire diameter
          2/22.8 = 0.0877 = 8.77% —-> 17.54% with respect the entire diameter

          And then see also what can be the relation between the inherent thickness of PCW, S1, S2 (on observed linen fibrils) and the results obtained using a different lenght of “penetration depth”.

          In other words:
          I am curious to know more about the criterion used to calibrate the ATR-FTIR penetration depth into the linen samples…
          This doesn’t appear in the book.

          Am I wrong in these simple “pre-optical remarks”?

  5. Hugh Farey
    September 14, 2015 at 12:37 pm

    “The STURP members invested significant time and resources because most of them believed in its authenticity.”

    Non-authenticists often say that the majority of the STuRP team were fundamental Christians who either thought the Shroud was genuine or fervently hoped it was genuine. Authenticists often counter this by pointing out members of the team who were not fundamental Christians. I don’t know how meaningful either of these statements are.
    Shroud.com lists 33 members of STURP, of whom 26 went to Turin in 1978. Some are virtually unknown (What did Rudolph Dichtl, Donald Janney, John German or Thomas Haverty actually do in Turin?), and the vast majority, having produced their report, do not seem to have involved themselves in the subject further. Joseph Accetta and Eric Jumper think the Shroud is medieval (although Jumper is reported as wavering on this recently), while Jackson, Bucklin, Rogers and Schwortz are/were on the side of authenticity. Even the authenticists, however, do not all see the Shroud as evidence of anything supernatural, especially the Jewish Schwortz, Adler and Devan. I don’t think the personal opinions and religions of the team are a fruitful line of inquiry.

    • September 16, 2015 at 12:27 pm

      Dear Hugh,
      This time I mostly agree with you. But please notice what a blog is: a personal diary. In this context (not in a scientific paper, of course) I think that some personal opinion are acceptable. When we read a book, there is always the biography of the author. I believe that knowing the life story of someone might be useful to better understand his writing. In this specific context (see how my post begins) to briefly discuss the personal opinions of STURP members it is appropriate. I fully agree that a scientific work should only be evaluated on the base of data, and nothing else.

  6. Louis
    September 14, 2015 at 1:35 pm

    No one is obliged to impose a belief on anyone else. Most Christians and some Jews (and not only Messianic Jews) believe in Jesus’ resurrection. Some pro-authenticists believe that the relic demonstrates a supernatural event, others don’t. In the latter group are those who believe that Jesus survived the crucifixion and went to India. To say that, in my view, is to judge Jesus to have been the greatest liar and trickster, or expert magician, in history. I did not see any of the “Shroudies” at the Hampshire event telling the people there that they got their history wrong. Alright, they chose to keep quiet. But, at least they could have asked them why they did not send a letter to Turin, asking the clerics to transfer the relic to any of the museums listed in the link:
    https://en.wikipedia.org/wiki/List_of_magic_museums
    ?

  7. Paulette
    September 14, 2015 at 1:38 pm

    So ends reweaving. Next idea?

    • September 14, 2015 at 1:40 pm

      Nothing ends -the Bella et al. editorial is a manipulation. Which can be shown.

  8. Thibault HEIMBURGER
    September 14, 2015 at 3:08 pm

    Nothing new!

    What is really shocking is what follows:

    1) the authors try to make believe that in Rogers’ paper “According to the Author [Rogers], however, the key evidence to support this thesis is the analysis of two pyrolysis spectra”.
    Rogers never said that.
    His analysis of the Py-MS spectra is just one of several evidence (cotton, vanillin, chemical testing).
    Rogers, contrary to the authors gathered several data before writing his paper.
    The authors worked only on 2 spectra and concluded that Rogers was entirely wrong !

    2) The authors did not take into account the proofs I gave regarding peak at mass= 131.
    They do not hesitate to repeat in their final paper their mistake based on a misunderstanding of a single sentence in Rogers’ paper.

    More seriously the authors wrote:
    “No diagnostic peak in the pyrolysis mass spectra indicates a significant difference in the two samples, besides hydrocarbon-derived contamination. Therefore, none of the presented data supports the conclusion by Rogers”.

    “No diagnostic peak in the pyrolysis mass spectra indicates a significant difference in the two samples, besides hydrocarbon-derived contamination.”
    Rogers would agree apart from the nature of the contaminant.

    About the nature of the contaminant:
    As a proof of their conclusion, the authors show an example of “mass spectra from a molecule with a long aliphatic chain(exadecan-1-ol), which fragmentation pattern is similar to the contaminant presents in the Raes sample (sample b)”
    They concluded that the contaminant in Raes spectrum IS an hydrocarbon-derived molecule.

    This conclusion is simply pseudo-science.

    It’s very easy to find many molecules from other species with a mass spectrum almost exactly similar to the Raes spectrum.

    It is a hard work and I am currently working with somebody who has much more knowledge of MS than me.

    Be sure that there will be an answer.

    • September 14, 2015 at 3:18 pm

      Yes, Thibault there will be an answer.
      You don’t have to even have an expertise in this field to show that this whole editorial is a pseudoscience. Just careful analysis of their wording and paper content…

      I wrote: “Bella et al. editorial is a manipulation. Which can be shown.”

      I have sent Dan some of my observations on that. I hope they will be published.

  9. anoxie
    September 15, 2015 at 1:01 am

    This is merely Rogers bashing, unsupported by facts obviously.

    • September 15, 2015 at 2:06 am

      That’s rich, coming from one of the usual suspects who routinely engages in Berry-bashing on this site.

      Here’s something else that will no doubt be portrayed as Rogers-bashing, when it’s nothing of the sort, and indeed is merely an essential part of the self-correcting process that is science. (The anoxies of this world simply do not understand how science works).

      Rogers claimed that the coloration of TS image fibres was confined to a highly superficial layer that could be retained by his Mylar adhesive tape when the fibre was plucked out with forceps. That’s become an essential part of TS orthodoxy – something one dare not challenge.

      Well, I’m going to challenge it. My flour imprints after washing with soap and water are faint, almost TS-like one might say, but are still easily visible. But when one examines under the microscope one sees scarcely any yellow colour except ever so faintly in bundles of longitudinal fibres. Individual fibres look essentially colorless. The same would have applied perhaps to Rogers, viewing highly light-reflective linen fibres longitudinally.
      What if there was colour inside the fibres, but one was prevented from seeing it by the light reflecting/refracting properties of flax fibres that are polyhedrons (5 – 7 sides) in cross-section?

      That would appear to be the problem, since the colour becomes easily visible when one views the fibres in cross-section (the latter responds well to photo-enhancement).

      No, I’m not going to display my microphotographs, thanks to the likes of that spivvy and insufferable Paolo Di Lazzaro who uses my pictures to make cheap shots at my expense about not knowing how to focus a microscope. He’ll have to find himself another fall guy if wishing to use this or other internet sites to further display his profound ignorance of photochemistry.

      Suffice it to say that the images one sees of thread cross-sections and.or angled mountings may well help elucidate the nature of the half-tone effect, discontinuities etc. Anyone here with a better microscope than mine (Hugh especially, judging by that recent picture of him with an upmarket binocular model) has only to to email me, and I’ll happily share with them my technique and preliminary pictures (no obligation) to do with as they wish.

      I’m only here for the science (but will continue to blow the whistle on bad science whenever I see it, indifferent to whether the perpetrator is living or now departed). Science has to self-correct. It’s why science so often works when other methods of enquiry have failed to yield unambiguous answers.

    • daveb of wellington nz
      September 15, 2015 at 2:09 am

      There is a more important target than Rogers. The true agenda is a pathetic attempt to support the spurious radiocarbon dating, and thus to discredit the Shroud as an authentic relic of Christ’s burial.

      • Sampath Fernando
        September 15, 2015 at 2:35 am

        What is this joke. Scientists are attacking each others work. As Daveb says there must be an agenda.

        Who is misinforming the world. Earlier eggs are bad now good for health. Coconut oil is worse now it is the best oil for health.

  10. Hugh Farey
    September 15, 2015 at 2:08 am

    “The Midwest Center for Mass Spectrometry (MCMS) at the University of Nebraska, Lincoln, made dozens of scans on different samples in 1981. […] Seven different samples underwent multiple analyses at MCMS. […] “Some of the samples came from areas of apparent blood flows, some from scorched areas, one (“the Zina thread”) was a complete yarn segment that had been withdrawn from the heel image area, one came from a pure image area, one came from a water stain in an image area, and several were modern reproductions of ancient linen technology.” From Rogers’s Thermochimica Acta paper.

    If we suppose the word “some” to mean “two” and “several” to mean a minimum of “three”, the seven samples mentioned in sentence two have become at least ten by the end of the quote.

    What does this mean, and, crucially, where are the scans? Rogers selected two to illustrate, from a Raes thread (who scanned that?) and from a “Shroud image fibre.”

    Carefully rereading Rogers’s paper (and in view of Nitowski’s comments about who had what in 1996), it is not apparent that he was in possession of any Shroud fibres when he investigated the patch hypothesis, not that he carried out, or had others carry out, any mass spectrometry at that time. All his experiments were microscopical and chemical, and all carried out on the Raes and radiocarbon sample fibres he had at the time. Any comparison with Shroud fibres and the Holland was with previous data. A comparison of more spectra might help to confirm or to refute his case. Does anyone know where it may be found?

    • Thibault HEIMBURGER
      September 15, 2015 at 3:39 pm

      See the matrix of samples analyzed at the MCMS p.53 of the book.

      “If we suppose the word “some” to mean “two” and “several” to mean a minimum of “three”, the seven samples mentioned in sentence two have become at least ten by the end of the quote.”
      I don’t understand at all what you mean.

      “(…) where are the scans?”
      I asked the same question to Barrie who is the custodian of the Rogers’collection.
      His answer:
      ” I did not find any spectra [on Rogers’ computer] and probably won’t because in those days the spectra were recorded by a chart recorder and not by a computer. There may be some additional data in the boxes of Rogers materials I have, but I have not had time to go through them (there are 8 large boxes).”

      But be sure that Rogers carefully analyzed the charts before writing his paper.

      • Hugh Farey
        September 15, 2015 at 4:32 pm

        “I don’t understand at all what you mean.” Over the course of a single paragraph, Rogers contradicts himself. How many samples were analysed? Why was he not precise?

        No. I am certainly not “sure that Rogers carefully analyzed the charts before writing his paper,” and even if he did, I should like to analyse them myself. However Barrie may be correct that they are in the boxes he left on his death, and I dare say we will have to wait until they can be examined. However, Rogers did say that polythene showed up on the scans, and Bella shows that one of the only two scans published shows a spectrum which would corroborate that.

        Meanwhile, was there only one copy of the scans made? Did Rogers not show them to anybody? This secrecy about what seems to me fairly important evidence is all very peculiar, don’t you think?

        • Thibault HEIMBURGER
          September 16, 2015 at 3:23 pm

          ” How many samples were analysed?”

          Seven.
          “Seven different samples underwent multiple analyses at MCMS”-Rogers.
          But some of them (Raes sample and perhaps modern samples) were likely divided and analysed separately (“Compared with fibers extracted from the sample tapes, there was ample material from the Raes sample …”).
          Is it important. No.

          “No. I am certainly not “sure that Rogers carefully analyzed the charts before writing his paper,” and even if he did, I should like to analyse them myself.”.

          So, when Rogers wrote (in his book): “Maps of all of the other samples were also obtained. They all showed the same difference in product ratios: the Raes sample was unique”.
          Do you really think what you wrote?
          You can disagree with Rogers’ interpretation of the spectra but you can’t suggest that he didn’t not look carefully at all of the data before writing his paper.

          ” However, Rogers did say that polythene showed up on the scans, and Bella shows that one of the only two scans published shows a spectrum which would corroborate that.”

          I will give an answer to Bella.
          But I can’t believe that you so much underestimate Rogers.

          “This secrecy about what seems to me fairly important evidence is all very peculiar, don’t you think?”

          No.There is no secrecy at all.
          What kind of secrecy?

          Thibault.

        • Hugh Farey
          September 16, 2015 at 5:02 pm

          Seven samples were analysed. SEVEN

          “Some of the samples came from areas of apparent blood flows” At least TWO.

          “some from scorched areas” At least TWO

          “one … was a complete yarn segment.” ONE

          “one came from a pure image area” ONE

          “one came from a water stain in an image area” ONE

          “several were modern reproductions of ancient linen technology.” At least THREE

          Not forgetting the Raes sample. Another ONE.

          “Maps of all of the other samples were also obtained. They all showed the same difference in product ratios: the Raes sample was unique.” Really? The scorched areas looked the same as the image areas which looked the same as the modern reproductions? But the Raes sample, whose spectrum showed the “parts per billion
          traces of oligomers from the polyethylene bag” was different from all of these. If Rogers’s supposed pentosan is correct, and Marco Bella’s polymer lines are incorrect, then where are the lines for the polyethylene bag which Rogers said were detected by the MS machine? I cannot find a spectrum for polyethylene on the internet, so am unable to confirm either Rogers or Bella in this respect.

          “Do you really think what you wrote?” Yes, I’m afraid I do. I cannot believe that I am the only person to be interested in the “dozens of scans on different samples” and yet there is no evidence even for their existence outside Rogers’s own comments. I do not for one moment believe the tests were not carried out, but I do think it beyond credibility that nobody apart from Rogers took any interest. It is becoming increasingly apparent to me that, undoubted expert though he was, Rogers was a bit of a maverick in Shroud circles, and I would not be at all surprised to hear that he kept his findings entirely to himself. In the absence of any information either way, neither I nor you nor anybody else can be sure what they showed, or how carefully they were analysed.

  11. Louis
    September 15, 2015 at 9:52 am

    Professor Marco Bella has correctly noticed that some people are mixing things up, as though depending on the authenticity of the Shroud to continue to believe in Jesus. I have had frank discussions about this point with prominent Shroudies and can confirm what he is saying. I cannot say anything about the professor’s beliefs, but the fact that at least one co-author of the paper is a well-known sceptic appears to have prompted some “Shroudies” to be suspicious about everything.

    What one can say with certainty is that Turin does not seem to take papers in Shroud research seriously and we cannot hope that any doors will be thrown open for another hands-on examination, or for another round of carbon dating.

    Oxford has said that its doors are open for carbon dating, however the differences in opinion about why exactly the 1988 results may have been skewed would have to be sorted out first. Professor Christopher Ramsey made that very clear:
    https://www.academia.edu/7893085/The_Quest_for_Jesus_in_Shroud_research

    In his last Shroud book “The Shroud.The 2000-year-old mystery solved” Ian Wilson provides a complete picture about what has gone on and even doubts that any solution can be reached, considering many things that have been published so far, and why the relic may not even be an artefact suitable for carbon dating.

    • September 15, 2015 at 9:55 am

      The first one who is mixing things up is “Professor” Marco Bella.

  12. Louis
    September 15, 2015 at 11:44 am

    The Church does not mix things up, it places emphasis on canonisation.
    Given the chaotic world we live in people are looking for responses, something “palpable” that can serve as a prop for faith.
    Good Father Francis O’Leary had a spiritual interpretation of the Jospice Mattress Imprint, with which I could not agree. Poor Mother Teresa spent a number of years doubting the existence of God, while carrying on the work she was doing. She discussed her doubts with Archbishop Perrier of Calcutta, but there is no record of her looking to relics for solace. She of course never really gave up her faith.
    The Church holds the Shroud expositions because of tradition, just as the “Veronica”
    is exhibited once a year in Saint Peter’s Basilica, Rome. For the rest:
    https://www.academia.edu/14795646/An_interview_with_Professor_Heinrich_Pfeiffer_SJ

    • Louis
      September 15, 2015 at 3:04 pm

      The Shroud does not seem to be on the agenda now. Canonisations sometimes take dozens of years and involve tons of documents and that also happens when a candidate has to be declared “Venerable”. For instance, it is the case of the Swiss Capuchin Archbishop Anastasius Hartmann, who was archbishop of Patna and Bombay, both cities in India:
      http://catholicsaints.info/venerable-anastasius-hartmann/

      • Louis
        September 16, 2015 at 4:34 pm

        Bono prays to Jesus and believes in….

  13. piero
    September 15, 2015 at 11:50 am

    I have observed (another time) the
    “oleic acid mas spectrometry” and then
    I have seen the presence same peaks:
    55 (but the right number that was shown in “Raes sample-fiber”
    [Fig. 5 from paper by Rogers] was 56 !!!), 69, 83, 97, 111.
    Also this (mass spectroscopy) diagram shows the “-CH2-” peaks…

    So…
    Is that a sufficient “proof” to disprove Ray Rogers or Marco Bella ?
    Yes or not?
    “No, or not completely…”, it’s my answer…

    Has been (Prof. Bella) trying to built a sort of
    chemical “crop circle” with his own
    interpretation of mass spectrometry
    (regarding that “Raes sample-fiber”) ?

    …and I then I reach the following conclusion:
    We have to be more careful when we want
    to work with mass spectrometry diagrams!

    Links:

    http://lipidlibrary.aocs.org/Analysis/content.cfm?ItemNumber=39508

    http://aocs.files.cms-plus.com/LipidsLibrary/images/Importedfiles/lipidlibrary/ms/ms21/file.pdf

    (page 2 of that file in .pdf format)

    — —
    Here an old (1980) reference:

    Computerized mass spectrum prediction and ranking
    N. A. B. Gray, R. E. Carhart, A. Lavanchy, D. H. Smith,
    T. Varkony, B. G. Buchanan, W. C. White, L. Creary

    Anal. Chem., 1980, 52 (7), pp 1095–1102

    Publication Date: June 1980

    Link:
    http://pubs.acs.org/doi/abs/10.1021/ac50057a023

    Other bibliographic references:

    1 – New Computer Aided Methods for Revealing Structural Features of Unknown Compounds Using Low Resolution Mass Spectra
    by
    Konstantin S. Lebedev and Daniel Cabrol-Bass

    J. Chem. Inf. Comput. Sci., 1998, 38 (3), pp 410–419

    Publication Date (Web): February 28, 1998
    Copyright © 1998 American Chemical Society

    2 – Automatic Spectra Interpretation, Structure Generation, and Ranking
    Patrick Fontana and Ernö Pretsch *
    J. Chem. Inf. Comput. Sci., 2002, 42 (3), pp 614–619

    Publication Date (Web): March 22, 2002
    Copyright © 2002 American Chemical Society

    3 – Optimization and testing of mass spectral
    library search algorithms for compound identification.

    S.E. Stein, D.R. Scott

    J. Am. Soc. Mass Spectrom., 5 (1994), pp. 859–866

    4- An integrated method for spectrum extraction and
    compound identification from gas chromatography/mass spectrometry data.
    by S.E. Stein

    Journal of the American Society for Mass Spectrometry
    Volume 10, Issue 8, August 1999, Pages 770–781

    — — —
    Do you know what is AMDIS?

    AMDIS – Automated Mass spectral Deconfolution and Identification System …

    I have found this acronym with the following link:
    http://www.nist.gov/oles/upload/11-Stein_Steve-Mass-Spec-Reference-Libraries-for-Forensics.pdf

    Links:
    http://chemdata.nist.gov/dokuwiki/doku.php?id=chemdata:amdis
    http://chemdata.nist.gov/dokuwiki/doku.php?id=chemdata:amdisexplained

    …AMDIS was developed at NIST for the critical task of verifying
    a major international treaty, the Chemical Weapons Convention. …

    The overall process involves four sequential steps:
    1 – noise analysis
    2 – component perception
    3 – spectral “deconvolution”
    4 – compound identification
    — — —
    Where are the experts in the field of mass spectrometry ?
    … Where are they (…secretly hidden?)?

    • September 15, 2015 at 2:07 pm

      Dear Piero,
      As I tried to suggest several times, go to someone you trust who knows mass spectrometry and bring Rogers paper. The expert will explain you why there is no significant difference between the two spectra, except the contaminant. Whatever it is, it should not be there. Please notice that olive oil does not generally contain oleic acid as such, but its ester with glycerol (triglyceride), and in every case there is no reason why it should be present in Raes sample.

      • September 15, 2015 at 2:26 pm

        One of us is not in the least bit surprised to see evidence (of sorts) for traces of olive oil (or one of more of its fatty acyl side chains) on the TS. A little vegetable oil makes flour imprinting off a human subject simpler and faster. The flour sticks better to oil-smeared skin, and as a bonus speeds up colour development in the oven.

        http://colinb-sciencebuzz.blogspot.co.uk/2015/08/is-high-energy-laser-beam-really-needed.html

        • September 15, 2015 at 3:06 pm

          dear Colin,
          I do not think it is olive oli. It is not on the image, but on a corner (Raes Sample) where there is no image.

      • Thibault HEIMBURGER
        September 15, 2015 at 2:48 pm

        Dear Marco,

        You wrote: “The expert will explain you why there is no significant difference between the two spectra, except the contaminant. Whatever it is, it should not be there.”

        I asked you many time in vain what is the difference with Rogers with the exception of the chemical nature of the contaminant.

        You both agree that the Raes sample is contaminated and that the contaminant, “whatever it is should not be there!”

        What do you mean exactly by “contaminant” ?
        Do you think that the Gum/Dye contaminant found by Rogers is not a contaminant in the sense you give this word ?
        If yes, please explain.

        • September 16, 2015 at 11:33 am

          Dear Thibault,
          Raes (textile expert) examined in 1973 the corner of the Shroud where the so called “invisible mending” should be. No evidence of mending. Vial and Testore (textile experts) decided in 1988 to cut the C14 sample nearby, because they were convinced the linen was all the same. They did not described any mending. After the Benford and Marino (no textile experts) hypothesis became popular, Flury-Lemberg (textile expert) analysed again that corner in 2002, and even the back of the cloth. She strongly denies that it any mending could be present. The proof of a mending there should be really strong.

          In Rogers paper, the only data we can check is the two mass spectra. They have little differences except for the cluster of peaks on the left differing by 14 atomic mass units. Please notice that dyes and natural gum (arabic gum is a mixture of glycoproteins and carbohydrates) would not give a similar spectra, while it is compatible with the presence on Raes sample of “oligomers from polyethylene”. Rogers wrote he actually detected them. Furthermore, what Rogers believed to be furfural (the peak at m=96), a decomposition product of pentosanes, it is actually just one of the peaks due to the contaminant.

          I thik that this is enough. Let’s Rogers rest in peace.

        • Thibault HEIMBURGER
          September 16, 2015 at 2:24 pm

          Thanks Marco,

          At least I have an answer.

          Some comments later.

        • Thibault HEIMBURGER
          September 17, 2015 at 3:21 pm

          Dear Marco,

          You wrote: “Please notice that dyes and natural gum (arabic gum is a mixture of glycoproteins and carbohydrates) would not give a similar spectra,…”

          I know what Arabic gum is.

          Are you sure that Arabic gum “would not give a similar spectra” ?
          I’ll show you probably the contrary (more work is needed).

          “… while it is compatible with the presence on Raes sample of “oligomers from polyethylene”

          In your paper you showed the example of ” “exadecan-1-ol” (in fact: “hexadecan-1-ol” or better: 1-Hexadecanol ).

          All of the MS spectra of this kind of compounds (including 1-Hexadecanol) show strong peaks between m/z= 40 and m/z=50 (particularly m/z= 43).
          If you look at Fig.5 in Rogers’paper there is absolutely no peak between m/z=40 and m/z= 49.
          Moreover some of these spectra do not show at all the pattern that is supposed to be “the characteristic peak pattern derived from the fragmentation of a molecule with a long hydrocarbon moiety”

          If the contaminant is what you think, how do you explain the lack of peak between m/z=40 and m/z=50 in Fig.5 of Rogers’paper ?

        • September 16, 2015 at 3:12 pm

          If that helps, we can use instead of “contaminant” the words “external contaminant”

        • September 18, 2015 at 12:33 pm

          Dear Thibauld,
          ———
          >In your paper you showed the example of ” “exadecan-1-ol” (in fact: “hexadecan-1-ol” or better: 1->Hexadecanol )
          ——-
          Correct. There is an “h” missing.

          ——————
          >All of the MS spectra of this kind of compounds >>(including 1-Hexadecanol) show strong peaks between >m/z= 40 and m/z=50 (particularly m/z= 43).
          >If you look at Fig.5 in Rogers’paper there is absolutely >no peak between m/z=40 and m/z= 49.[….]
          >If the contaminant is what you think, how do you >explain the lack of peak between m/z=40 and m/z=50 >in Fig.5 of Rogers’paper ?
          ————–
          This is actually a very good observation. It is correct that there should be a peak around M=43, while there is absolutely nothing below M=49. However, we should take into account the instrument used and the settings.
          Rogers wrote:

          ———–
          …The chemical-ionization system used was the most sensitive MS at the time, sufficiently sensitive to detect parts per-billion traces of oligomers from the polyethylene bag that Gonella had used to wrap the Raes threads. The instrument at MCMS is equipped with a pulsed source…
          ———-
          Since there is absolutely no other peak below M=49, it is most likely that the instrument was set to not acquire this part of the spectra. This is very common, because the peaks at low masses have little diagnostic value and their intensity might interfere with the other peaks, so it is better to cut them. If you see the spectra above, (fig 4), this is recorded without the zone below M=49. To be absolutely sure, one must see all instrumental setting (Which Rogers did not report).

        • Thibault HEIMBURGER
          September 18, 2015 at 3:23 pm

          Dear Marco,

          You are right.

          I have found the proof that the the instrument was very likely set not to acquire data below m/z=50.
          The proof is found in his book (p.56-57) where two mass/scan/intensity 3D maps are shown (sample 1EB and Raes sample)
          In both cases, the origin of “mass data” is 50.

          But do you consider my finding relevant, since I found it in his book and not in his paper ?

          More seriously, regarding the “Scan/mass/intensity map” (Fig. VIII-6 in Rogers’book: Raes sample), Rogers wrote: ” The m/e 96 peak for furfural appears relatively early, and it disappears quickly”.

          Whatever m/e=96 is, this is an important observation:this peak “disappears quickly”.
          It should be interesting to have more spectra from 1-Hexadecanol at different temperatures.

      • Mario Latendresse
        September 16, 2015 at 3:26 pm

        Marco Bella wrote:

        “… there is no significant difference between the two spectra, except the contaminant. Whatever it is, it should not be there.”

        But then a few days later you wrote “it is compatible with the presence on Raes sample of “oligomers from polyethylene””.

        So, your determination of the M-n14 peaks are definitively oligomers from polyethylene? I would revise this statement, see for example

        http://www.sciencedirect.com/science/article/pii/S0142941812000256

        The mass spectra would have m/z values way above 500 for oligomers coming from polyethylene. Besides, this polyethylene contaminant should be so small that the spectra of the pyrolysis of the sample itself would have the major abundances, not the other way around.

        When you wrote your editorial publication you only gave a very general class of molecules for the contaminant (long hydrocarbon chains), which I believe is the only possible conclusion given the lack of more mass spectra at/of different times/temperatures. A more precise determination would require an identification of the other peaks, in particular peak m/z 131, which you have not identified its provenance.

        But more importantly, your determination of the abundance of m/z 96 coming from the “contaminant” is unproven in your publication because until you know the other molecule(s) involved in that spectra (and the exact “contaminant” molecular structure), you cannot determine the relative abundance for the m/z 96 peak coming from the “contaminant”. It can be a combination of two or more fragments of two or more different molecules interfering in the mass spectra.

        Also, your statement that the relative abundance of m/z 126 would be non zero when removing that “contaminant” spectra is odd. The mass spectra shows a relative abundance of zero for m/z 126, and this is all that can be said.

        In summary, your statement that the two mass spectra are identical once the “contaminant” mass spectra is removed is at least very approximate but essentially unproven.

        And what you consider a “contaminant” can actually be coming directly from the sample, in particular from sebum, which is mostly made of lipids, and the fact that this section of the Shroud has been heavily hand manipulated to hold and display the Shroud.

        • September 16, 2015 at 4:48 pm

          Dear Mario,

          I will try to answer your questions, but please, as said to others, seek the advice of someone who is expert in mass spectrometry before trying to attempt to formulate hypothesis.

          DIY does not really work in science.

          The first paper you linked (have you actually read it?)
          http://www.sciencedirect.com/science/article/pii/S0142941812000256

          Speaks about polyethylene TEREPHTHALATE, or PET. This is the plastic used to make bottles. This polymer DOES NOT have long aliphatic chains, but has
          (-CH2CH2-) units linked to phthalate.

          Polyethylene instead, is the material used to make plastic bags, and this contains long aliphatic chains.

          Names might sound similar but they are different molecules. Just check on wikipedia the difference.

        • September 20, 2015 at 12:42 am

          Dear Mario,
          Here it is the rest of my answer.

          1)
          ————-
          >When you wrote your editorial publication you only >gave a very general class of molecules for the >contaminant (long hydrocarbon chains), which I believe >is the only possible conclusion…
          ———–
          I agree. With the reported spectra we cannot identify more precisely the contaminant. However, oligomers of polyethylene would actually give compatible spectra.

          2)
          ———
          >more precise determination would require an >identification of the other peaks, in particular peak m/z >131, which you have not identified its provenance.
          ——-
          Correct, but the fact that this peak is present as the major peak in both spectra (not considering contamination) points towards identity of the two samples, therefore actually denying the “medieval invisible mending” theory.
          Please notice that it is Rogers which should have given evidence about the “invisible mending”.
          Let’s assume you affirm that there is a “pink invisible dragon” in your garage which only you can see, giving only a very confused photo. Your job is to demonstrate this statement; my job is just to say that the photo is really confusing and that there is no evidence.

          3)
          ——–
          >But more importantly, your determination of the >abundance of m/z 96 coming from the “contaminant” >is unproven in your publication..etc
          ………..
          This is unproven in Rogers’ paper. Surely, the contaminant would have this peak, and we do not have any element to say it is furfural. See also “pink dragon” argument, answer #2.

          4)
          ———
          >Also, your statement that the relative abundance of m/z >126 would be non[-]zero when removing that >“contaminant” spectra is odd…
          ——–
          Again, this is Rogers’ problem, not mine. If the relative abundance of a peak is too low, it would not be quantified in mass spectra. Rogers, in order to show the absence of the peak at M=126 should have taken a cleaner spectra, where the major peak would be in both the one at M=131. Since this was not done, again we do not have any evidence. See “pink dragon” argument, answer #2.

          5)
          ——
          >In summary, your statement that the two mass spectra >are identical once the “contaminant” mass >spectra is >removed is at least very approximate but essentially >unproven.
          ——-
          It is Rogers that should had given clear evidence about the “invisible mending”. See “pink dragon” argument, answer #2. The statements of Rogers regarding the “invisible mending” are not only unproven, but also denied by his own data.

          6)
          ———-
          >And what you consider a “contaminant” can actually be >coming directly from the sample, in particular >from >sebum….
          ———-
          This is very interesting because it demonstrate how Shroud scholar underestimates the consequences of their hypotheses. I agree: sebum (contains triglycerides) is compatible with the spectra of the contaminant. But if there is really sebum, that means that Rogers was not only once, but twice wrong. First, when he thought that there were oligomers from polyethylene, and second when he thought that the two samples were different. If the contaminant would be sebum, the “invisible mending hypothesis” is then denied.

      • Mario Latendresse
        September 23, 2015 at 3:35 am

        Dear Marco,

        It appears that you are assuming that I think that the analysis of the Raes spectrum by Rogers confirms that gum Arabic is present on the sample he studied. I do not think that.

        My first point is that there is not enough information provided with the spectrum to do its full analysis, in particular the temperature at which the spectrum was created and the energy of the ionization that was used for that spectrum. Also, it would require several spectra of that sample at different time during pyrolysis to help confirm the identity of the molecules involved.

        On the other hand, the spectrum is not very far from what Rogers concluded, in particular, furfural appears present in that spectrum and the intensity at m/z 126 is negligible.

        My second point is that you made an error by over interpreting that spectrum, in particular by asserting that by removing what you call the “contaminant” you would get the same spectrum as the image-only sample. But without identifying precisely that contaminant, it is not possible to come to that conclusion. You would need to quantify every peak of the contaminant, which you have not done, and which is not even possible to do given this single spectrum.

        You also made a clear call on m/z 126, stating that it would become a value similar to the spectrum from the image-only sample once the contaminant was removed. But, this is arithmetically impossible, if you do some simple calculation, whatever that contaminant is. (multiple by 4 (the ratio for m/z 131 between the two spectra) the near zero value of m/z 126, and you certainly cannot get close to 25 as in the image-only spectrum.)

        In other words, something else appears at play with that spectrum and it could be what Rogers concluded or something more complex: gum Arabic mixed with sebum and some cellulose, or gum Arabic with some other material, or sebum with cellulose, etc.

        Also, let’s not forget that the gum Arabic identification in Rogers’ paper was not based only on the spectrum. So a full appreciation of its conclusion is not strictly based on that spectrum.

        How do you classify “pseudo-science”? Would an invalid manipulation of a spectrum be classified as “pseudo-science”?

        • September 25, 2015 at 1:33 pm

          Dear Mario,
          Regarding Arabic gum, here it is what Rogers wrote:

          ————-
          A gum/dye/mordant coating is easy to observe on Raes and radiocarbon yarns. No other part of the shroud shows such a coating. The early thermal evolution of furfural during pyrolysis/ms analyses, the relatively easy water solubility, the yellow color formed with iodine, and the easy hydrolysis suggest gum Arabic. Gum Arabic is obtained from Acacia senegal and is composed of pentose-sugar units. Its presence as a major component in the coatings on the Raes and radiocarbon samples is not a surprise, because it has long been a common vehicle in tempera paints. The radiocarbon sample had been dyed. Dyeing was probably done intentionally on pristine replacement material to match the color of the older, sepia-colored cloth…

          ————–

          So, the presence of Arabic gum is “suggested” by:
          1) “thermal evolution of furfural [peak at M=96] during pyrolysis”> the peak at M=96 belongs to the cluster of the contaminant and, as said many times, could be many different things. A single peak in mass spectrometry is not enough to confirm anything.
          2) “Relatively easily [relatively respect to what?] water solubility”, you tell me which significance that has. Millions of substance dissolve in water, starting from salt and sugar.
          3) “yellow color formed with iodine” Millions of compounds form a yellow color with iodine, therefore it is used in most chemistry laboratories around the world to stain the TLC spots.
          You tell me how reliable this identification is.

          You also wrote:
          ———–
          >On the other hand, the spectrum is not very far from >what Rogers concluded, in particular, furfural [the >peak at M=96] appears present in that spectrum and >the intensity at m/z 126 is negligible.
          ———-
          Please refer again to the “pink dragon argument” illustrated above. Find someone that knows how mass spectrometry works and ask how confident would the expert be to say that “…the spectrum is not very far from what Rogers concluded…”

          ————
          >My second point is that you made an error by over >interpreting that spectrum…

          ————
          The title of our editorial is “There is no mass spectrometry evidence that the C14 sample from the Shroud of Turin comes from a “medieval invisible mending”. Please refer again to the “pink dragon argument”. What about the interpretation of Rogers? Can we speak of over interpretation here, should we use your standard? Do you really think he did present convincing arguments to dismiss what the textile experts stated after direct analysis of the Shroud?
          ————

          >You also made a clear call on m/z 126, stating that it >would become a value similar to the spectrum from >the image-only sample once the contaminant was >removed. But, this is arithmetically impossible if you do >some simple calculation, whatever that contaminant is. >(multiple by 4 (the ratio for m/z 131 between the two >spectra) the near zero value of m/z 126, and you >certainly cannot get close to 25 as in the image-only >spectrum.)
          ————

          Again, go to an expert in mass spectrometry and ask. Briefly, response is not linear in mass spectrometry, and the ratio of peaks intensity changes with pyrolysis temperature (which Rogers did not report), so your argument is meaningless. Don’t DIY in science.

          —————
          >In other words, something else appears at play with >that spectrum and it could be what Rogers concluded…
          ————–
          Nothing can be concluded if you do not have enough evidence. The pyrolysis mass spectra have been taken in the eighties and left in a drawer for about twenty years. They resurfaced only to support the “invisible mending” theory. Why? Reasoning in the same way Rogers did in his paper I could easily say that there is an invisible pink dragon in my garage.

          About pseudoscience, here it is what is written on Wikipedia:
          —————
          Pseudoscience is a claim, belief or practice which is incorrectly presented as scientific, but does not adhere to a valid scientific method, cannot be reliably tested, or otherwise lacks scientific status. Pseudoscience is often characterized by the use of vague, contradictory, exaggerated or unprovable claims, an over-reliance on confirmation rather than rigorous attempts at refutation, a lack of openness to evaluation by other experts, and a general absence of systematic processes to rationally develop theories.
          A field, practice, or body of knowledge can reasonably be called pseudoscientific when it is presented as consistent with the norms of scientific research, but it demonstrably fails to meet these norms.
          ————

          Decide by yourself what can be considered pseudoscience among “invisible mending theory”, Rogers’ paper and our editorial, using as benchmark the above definition.
          Why not just accepting the statement/title of the editorial “there is no evidence etc.”, forget about whatsoever “invisible mending” and let Rogers rest in peace?

        • September 25, 2015 at 3:24 pm

          About pseudoscience, here it is what is written on Wikipedia:
          —————
          Pseudoscience is a claim, belief or practice which is incorrectly presented as scientific, but does not adhere to a valid scientific method, cannot be reliably tested, or otherwise lacks scientific status. Pseudoscience is often characterized by the use of vague, contradictory, exaggerated or unprovable claims, an over-reliance on confirmation rather than rigorous attempts at refutation, a lack of openness to evaluation by other experts, and a general absence of systematic processes to rationally develop theories.
          A field, practice, or body of knowledge can reasonably be called pseudoscientific when it is presented as consistent with the norms of scientific research, but it demonstrably fails to meet these norms.
          ————

          Decide by yourself what can be considered pseudoscience among “invisible mending theory”, Rogers’ paper and our editorial, using as benchmark the above definition.

          Your editorial, Marco. Obviously.

          Don’t teach your grandmother how to suck eggs.

  14. piero
    September 16, 2015 at 11:51 am

    Altough I had noticed some vague similitudes
    (= few peaks), I don’t believe in “Olive oil” as
    true solution of the “identification problem”…
    and then I agree with Marco Bella
    (= “I do not think it is olive oil”)…
    and that starting only from the m/s diagram
    and not for other explanations (such this =
    “…It is not on the image, but on a corner
    (Raes Sample) where there is no image”).

    Since Mass Spectra are reproducible,
    I think we have to check (= searching in
    the mass spectra library) what is the possible
    Spectrum that exactly matches our mass
    spectroscopy diagram we have to interpret.

    Stop.
    This can be the work to do.
    In my opinion, this problem is even trivial!

    So…
    Where are your own results?
    -*-*-*-*-*-*-
    Here what we can see under the address:
    http://www.kayelaby.npl.co.uk/chemistry/3_8/3_8_6.html

    regarding the problem of identification for
    “mass spectra obtained from the pyrolisis of a Raes sample-fiber”

    m/z = 55
    Possible associated group = C3H3O
    Possible inference = Some cyclic ketones

    … but we haven’t this number of mass,
    instead we clearly read the numebr 56

    m/z = 56
    Possible associated group = C4H8
    Possible inference = Hydrocarbon

    m/z = 69
    Possible associated group = C5H9
    Possible inference = Some Hydrocarbons

    m/z = 83
    Possible associated group = C4H3S
    Possible inference = Monosubstituted thiophenes

    But it seems hard to believe to the presence
    of sulfur and then it would seem that this peak
    was due to the repetition of known period n = 14
    (= CH2 = 12 + 2) …

    m/z = 97
    Possible associated group = C5H5S
    Possible inference = Methyl or mono-alkyl thiophenes

    m/z = 131
    Possible associated group = C6H5CHCHCO
    Possible inference = C6H5CHCHCOX

    In any case, this analysis seem to be very rough…

    And then take into account that at 85 we have also
    the possible furanic ring (with 2 Oxygen,
    one into the ring and the other out)!

    Link:
    https://en.wikipedia.org/wiki/Furan

    Links about Furfural m/s :

    http://webbook.nist.gov/cgi/cbook.cgi?ID=C98011&Mask=200

    http://webbook.nist.gov/cgi/cbook.cgi?Spec=C98011&Index=0&Type=Mass&Large=on

    • piero
      September 17, 2015 at 11:18 am

      Errata corrige:
      >Although

      instead of:
      >Altough
      — — *** — —
      Yesterday I was disturbed.
      — — —
      Here what I want to add:
      in the paper by Dr. Ray Rogers
      “Pyrolysis/Mass Spectrometry applied to the Shroud of Turin”
      there is a tridimensional diagram
      (=”mass/scan/concentration map of the pyrolysis products”)
      about the sample “Shroud-image fiber”
      (Slide Number: “E1B”),
      but there is not a tridimensional diagram
      for the other sample (Slide Number: “Raes #3”),:
      “mass spectra obtained from the pyrolisis
      of a Raes sample-fiber”…
      So…
      in my opinion, we cannot discuss
      in a deep manner the entire issue.

      Sorry. I have just seen that the paper:
      http://www.shroud.it/ROGERS-3.PDF
      is a bit different (= there is no diagram about the
      “mass/scan/concentration map of the pyrolysis products”)
      with respect the paper I had read years ago
      (and then this is under the Link:
      https://www.shroud.com/pdfs/rogers4.pdf).
      I beg your pardon!

      Perhaps Joan can help us.
      In any case I am curious about
      the probable paper written by “OK”…
      Also Thibault seems to be promising, but
      (until now) we have no exact interpretations,
      apart my goofy attempt (of yesterday)…
      and then here
      (regarding the boring problem of identification of
      “mass spectra obtained from the pyrolisis of a Raes sample-fiber”)
      I want to add the following (presumed) peaks:

      m/z = 73
      Possible associated group = C4H9O
      Possible inference = Alcohols, ethers
      my comment: it’s possible…
      — —
      But, see also:
      Xylose, that is a component in hemicellulose…

      >… cellulose contains only anhydrous glucose.
      >For instance, besides glucose, sugar monomers
      in hemicellulose can include xylose,
      mannose, galactose, rhamnose, and arabinose. …
      (Link: https://en.wikipedia.org/wiki/Hemicellulose )

      Xylose,
      with main m/z = 73 (other peaks at:
      31 [29,30; 32], 43 [41, 42,; 44, 45], 60, 61 and 71, 72 ; 74)

      Ref.:
      http://webbook.nist.gov/cgi/cbook.cgi?ID=C58866&Mask=200

      my comment:
      probably there is a very low percentage of xylose
      in linen fibrils (…but I have read that
      “Cellulose” from cotton (!) contain near 1.5% of xylose
      and smaller amounts of other monosaccharides…).
      Probably there is a risk greater than an
      extraction from “raffle drum” (= caos) with
      this kind of interpretation of spectra of mass spectrometry …
      — —
      m/z = 81
      Possible associated group = C5H5O
      Possible inference = Furans
      my comment: possible/probable

      m/z = 131
      Possible associated group = C6H5CHCHCO
      Possible inference = C6H5CHCHCOX
      my comment: unlikely…
      — —
      Few words about:
      Hydroxymethylfurfural = HMF
      main M/S peaks at:
      41 (and 39), 69, 97, 128 (?)

      Ref:
      http://webbook.nist.gov/cgi/cbook.cgi?ID=C67470&Mask=200

      my comment: possible but unlikely because
      Rogers wrote:
      “The hydroxymethylfurfural deformylates
      (loses a formaldehyde fragment) …”
      (https://www.shroud.com/pdfs/rogers4.pdf).

      Instead Furfural
      has the main peaks at:
      29 (little), 39 (and, less, 38), 67 (very little), 97 and 98
      (and both these [that nearly are “twin peaks”] are great peaks)

      Ref. under:
      http://webbook.nist.gov/cgi/cbook.cgi?ID=C98011&Mask=200

      I think we have to deepen the analyses about
      the questions regarding the 95, 96, 97, 98 peaks
      (I believe this can be another “key area” to investigate,
      after the other: 69, 131 169, 181 of “Shroud-image fiber”
      [“E1B”], and the series: 56-69-83-97
      of “Raes sample-fiber” [“Raes #3”]).

      Well, under:
      http://airborne.co.nz/hmf.shtml

      we can read:
      >…today HMF is used as an indicator of heating
      or storage at elevated temperatures … (of honey)

      >Hydroxymethylfurfural (HMF), also
      5-(Hydroxymethyl)furfural, is an organic
      compound derived from dehydration
      of certain sugars…

      Link:
      https://en.wikipedia.org/wiki/Hydroxymethylfurfural

      The acid-catalyzed dehydration
      of hexoses results in the formation of
      5-hydroxymethylfurfural (HMF).
      This is a well known fact.

      Colin,
      Here some “obvious words”
      (around “HMF and heat”) that (perhaps)
      can sound as familiar to your Food Chemistry:

      A) 5-Hydroxymethylfurfural (HMF), a
      heat-induced food toxicant present in a
      vast number of food items, has been suggested
      to be genotoxic after being bioactivated by
      the sulfotransferase SULT1A1 …

      B) 5-(Hydroxymethyl)furfural (HMF),
      one of the major intermediate products in
      the Maillard reaction, is present in a wide
      variety of foods. This aldehyde is formed as
      a decomposition product of glucose and
      fructose in foodstuffs subject to cooking or
      heat sterilization. …

      C) 5-Hydroxymethylfurfural (HMF),
      formed by acid-catalyzed dehydration and
      in the Maillard reaction from reducing sugars,
      is found at high levels in numerous foods. …

      Here a vague suggestion :
      Can be possible a series of reactions
      that includes Hydroxymethylfurfural and
      cadaveric emissions?
      This imply the role of a certain amount of heat
      (…seemingly as coming not from the corpse,
      because HMF is produced at certain “high temperature”!)
      — —
      Dan,
      have you a new useful answer for us
      (regarding Mass Spectrometry and “Raes sample”)
      on this blog?

  15. piero
    September 17, 2015 at 11:44 am

    3-Furaldehyde

    Formula: C5H4O2
    Molecular weight: 96.0841

    Mass Spectrum,
    peaks at:
    29 67 (very little), 39 (little) and (great) 97, 98

    Link:
    http://webbook.nist.gov/cgi/cbook.cgi?ID=C498602&Units=SI&Mask=FFFFFF

    — —
    Furfural, peaks at:
    29 (little), 39 (and 38) , 67 (very little), 97 and 98 (great)

    link:
    http://webbook.nist.gov/cgi/cbook.cgi?ID=C98011&Mask=200

  16. piero
    September 18, 2015 at 9:16 am

    I have found a different kind of “example”
    about the 55-69-83-97 peaks
    and then this is a bit different with respect the
    presumed (and strange) “polyethylene olygomers”.
    It’s “The mass spectrum of
    methyl 7-methyl-hexadec-6-enoate (from a
    jellyfish in this instance, but often present in fish
    from warm seas).
    But (in my opinion) “Branched-Chain Monoenoic Fatty Acids”
    have nothing to do with the interpretation of
    mass spectroscopy for the sample we have to check.

    Link:
    http://lipidlibrary.aocs.org/content.cfm?ItemNumber=39487

    In any case this kind of search in the field
    of mass spectrometry is only a waste of time…
    Continuing on this way,
    I think that I can only lose in this
    “game of individuation” for mass spectroscopy!

  17. Thibault HEIMBURGER
    September 19, 2015 at 1:09 pm

    Finally, I fully disagree with myself :-)

    Correction to my previous comment:

    The Raes sample shows a (very small) peak at m/z=49.

    The fact that the 3-D scan/mass/intensity maps begins at m=50 in Rogers’ book does not mean, contrary to what I wrote, that no data were acquired bellow 50.

    The other possibility is described by Marco: “Since there is absolutely no other peak below M=49, it is most likely that the instrument was set to not acquire this part of the spectra. This is very common, because the peaks at low masses have little diagnostic value and their intensity might interfere with the other peaks, so it is better to cut them. If you see the spectra above, (fig 4), this is recorded without the zone below M=49. To be absolutely sure, one must see all instrumental setting (Which Rogers did not report).”

    This argument is specious.

    The abscissa in Fig.4 (Shroud sample 1-EB) begins at m=50 and ends at m=220 (in fact data were acquired up to 500 or even 750).

    The abscissa in Raes spectrum begins clearly at m=40.
    If the instrument was set not to acquire the part of the spectrum between 40 and 50, why would Rogers show the part between 40 and 50 (without any signal, except at m=49) ?
    This abscissa should begin at 50, as in Fig.4.

    Moreover, if there were strong peaks around m=43 (like in the spectra of any molecule with a long aliphatic chain), they would certainly have been showed by Rogers. He would not have “cut them”.

    The FACT is that in the Raes spectrum there is really absolutely no signal between m=40 and m=48, something which is a huge problem for the hypothesis of the “long aliphatic chain contaminant” hypothesis.

    We have the spectrum of the Raes sample.
    We must examine it as such, without any kind of “ad-hoc” speculation.

    • September 19, 2015 at 2:21 pm

      And any possible implications of that?

      • Thibault HEIMBURGER
        September 19, 2015 at 2:49 pm

        Yes.
        It implies that the paper in question is biased.
        Much more tomorrow.

  18. piero
    September 20, 2015 at 8:28 am

    Here a vague idea about the peak at 69.

    Do you know what is Squalene?
    Squalene mass spectrum shows a peak at 69
    (and other [more little] peaks at: 81, 41 and 95)…

    Links:

    http://webbook.nist.gov/cgi/cbook.cgi?ID=C111024&Mask=200

    https://en.wikipedia.org/wiki/Squalene

    Sebum (and the Shroud taken by hands during the past):

    >Sebum, secreted by the sebaceous gland in humans, is primarily composed of triglycerides (~41%), wax esters (~26%), squalene (~12%), and free fatty acids (~16%). The composition of sebum varies across species. Wax esters, like squalene, are unique to sebum and not produced anywhere else in the body. Sapienic acid is a sebum fatty acid that is unique to humans, and is implicated in the development of acne.
    >Sebum is odorless, but its breakdown by bacteria can produce strong odors. …

    Link:
    https://en.wikipedia.org/wiki/Sebaceous_gland

    • piero
      September 21, 2015 at 10:05 am

      I want to add that in the book by Ray Rogers
      there is a comparative table about the
      sebaceous excretions of Homo Sapiens
      (= comparisons with respect other animal species)…
      — —
      I believe that isoprenic fragments (-C5H9)
      can also be found in mas spectra of natural gum
      (natural gum is a polymer based on isoprene units).
      In other words the C5H9-fragment (prenyl) is located
      at m/z 69 and this is an interesting fact…

      Do you remember the past “identification”?
      m/z = 69
      Possible associated group = C5H9
      Possible inference = “Some hydrocarbons”
      — —
      If we are able to work in the field of advanced microscopy,
      perhaps we can think to improve the investigations about
      the issue (= presumed presence of natural gum)
      starting from the other possible presence of
      mesophilic rubber-degrading bacteria G. polyisoprenivorans
      (= a rubber degrading actinomycete) …

      Reference :
      Case Report.
      A rubber-degrading organism growing from a human body
      by Mohit Gupta, Deepali Prasad, Harshit S. Khara, David Alcid

      International Journal of Infectious Diseases
      Volume 14, Issue 1, January 2010, Pages e75–e76

      Link:
      http://www.sciencedirect.com/science/article/pii/S1201971209001416

      Another reference:
      Gordonia polyisoprenivorans sp. nov., a rubber-degrading
      actinomycete isolated from an automobile tyre.
      by A. Linos, A. Steinbuchel, C. Sproer, R.M. Kroppenstedt

      Int J Syst Bacteriol, 49 (1999), pp. 1785–1791
      —- —-
      Other words about the “rubber-degrading bacteria
      G. polyisoprenivorans”:

      >Gummi abbauende Mikroorganismen können quantitativ an verschiedene praxisrelevante Gummimaterialien anheften.
      >Zum ersten Mal konnten Gummi abbauende Mikroorganismen (Gordonia westfalica, Gordonia polyisoprenivorans) mit dem AFM visualisiert werden, die an verschiedene Gummimaterialien angeheftet waren.

      Link:
      http://www.analytik-news.de/Dissertation/Brill-Florian-H.-H..html

      Here a very rough translation:
      >Rubber degrading microorganisms can attach
      to quantitatively different practice-oriented rubber materials.
      >For the first time rubber was degrading microorganisms (Gordonia westfalica Gordonia polyisoprenivorans) are visualized with the AFM, which were attached to various rubber materials.
      — —
      But all this talk about the possible
      presence of natural gum (…and
      inherent degrading microorganisms) is
      just pure speculation!

  19. December 18, 2015 at 1:38 pm

    A short communication answering the Bella et al. paper on the mass spectrometry analysis by Ray Rogers of fibers of the Raes sample has been accepted to be published in Thermochimica Acta.

    See http://www.sciencedirect.com/science/article/pii/S0040603115004724

    The final version should be posted soon by the publisher.

    I will post a summary and a draft version of this communication at http://www.sindonology.org in a week, that is, on Christmas day.

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