Lignin and Vanillin on the C14 Shroud of Turin Samples

Sensitive microchemical tests prove that Shroud of Turin is older than carbon 14 dating suggests.

Microchemical tests reveal vanillin (C₈H₈O₃ or 4-hydroxy-3-methoxybenzaldehyde) in an area of the cloth from which the carbon 14 sample were cut. But the rest of the cloth does not test positive for it.  Vanillin (vanilla) is produced by the thermal decomposition of lignin, a complex polymer, a non-carbohydrate constituent of plant material including flax. Found in medieval materials but not in much older cloths, it diminishes and disappears with time. For instance, the linen wrappings of the Dead Sea scrolls do not test positive for vanillin. (The kinetics constants for calculating the loss of vanillin from lignin are E = 29.6 kcal/mole and Z = 3.7 X 10exp11/second).

Quantitative counts of lignin residues show some large differences between the carbon 14 sampling areas and the rest of the Shroud. Where there is lignin in the sample area it tests positive for vanillin. Other medieval cloths, where lignin is found, test positive.  The main body of the Shroud, with significant lignin at the fiber growth nodes, does not have vanillin. The Shroud's lignin is very old compared with the radiocarbon sampling area. 

This is an important find. It suggests that the tested samples were possibly much newer and it underscores that the chemical nature of the carbon 14 samples and the main part of the cloth are outstandingly different.

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According to the carbon 14 (C14) dating results in 1988, the Shroud was not, as so many believed, the authentic burial Shroud of Jesus. It was medieval. Nature, the prestigious international weekly journal of science, published an article about the tests, coauthored by twenty-one scientists from the University of Oxford, the University of Arizona, the Institut für Mittelenergiephysik in Zurich, Columbia University, and the British Museum. The conclusion in Nature was clear:

The results of radiocarbon measurements at Arizona, Oxford and Zurich yield a calibrated calendar age range with at least 95 confidence for the linen of the Shroud of Turin of AD 1260 - 1390 (rounded down/up to nearest 10 yr). These results therefore provide conclusive evidence that the linen of the Shroud of Turin is mediaeval.

A headline in the New York Times read: “Test Shows Shroud of Turin to be Fraud.” Other newspapers around the world reported similar conclusions. One of the C14 dating scientists from Oxford stated on public television: “We have shown the Shroud to be a fake. Anyone who disagrees with us ought to belong to the Flat Earth Society.”

How can anyone doubt this?

Some researchers did. There was, after all, a significant amount of scientific and historical evidence that argued that the Shroud was certainly much older. And this resulted in speculation about why the results might be wrong; some of it absurd.  One hypothesis -- one that gets a lot of play in the press -- is that a microbiotic growth, a biopolymer, found on some archeological artifacts may be present on the Shroud. But it is highly questionable that there can be sufficient quantity of this newer material to alter the measurements enough to make a first century cloth seem medieval. Based on estimates that the polymer would need to be as much as 87% of the weight of the cloth, one wonders if the Shroud would not look more like a plasticized drop cloth than a delicate piece of linen. Another proposal was that that high temperatures from a fire in 1532, which damaged and nearly destroyed the Shroud, enhanced the mix of radioactive C14 and stable C12 isotopes in the cloth. This, if true, would make the cloth seem newer than it is. But experiments to test this idea have not been promising and are difficult to explain scientifically.

Recent, thorough, well-documented and confirmable studies by several researchers explain why the radiocarbon dating was incorrect. These were reported by National Geographic News and PBS in April 2004 as well as in scientific papers.

Scientists, now, so completely dispute the carbon 14 dating of the Shroud that it can no longer be considered meaningful. No one is disputing the quality of work done by the three labs. And no one is questioning the accuracy of C14 dating.

Discovery of a Medieval Repair Patch

M. Sue Benford and Joseph Marino, in collaboration with number of textile experts, identified clear evidence of medieval mending on the Shroud. A patch, it was found, was expertly sewn to or rewoven into the fabric to repair a damaged edge. It was from this patch—quite likely nothing more than a piece of medieval cloth expertly woven into the main body of the cloth—that the samples were taken. From documenting photographs of the sample areas, the textile experts identified enough newer thread to permit Ronald Hatfield, of the prestigious radiocarbon dating firm Beta Analytic, to estimate that the true date of the cloth is much older—perhaps even 1st century.

Independently, Anna Arnoldi of the University of Milan and Raymond N. Rogers, a Fellow of the University of California Los Alamos National Laboratory have explored the chemical nature of the sample area. They have confirmed the finding of Benford and Marino. Ultraviolet photography and spectral analysis show that the area from which the samples were taken was chemically unlike the rest of the cloth. Chemical analysis reveals the presence of Madder root dye and an aluminum oxide mordant (a reagent that fixes dyes to textiles). These dyestuffs are not found elsewhere on Shroud. Medieval artisans often dyed threads in this manner, using these very materials, when mending damaged tapestries. This was simply to make the repairs less noticeable.

This photograph, by Vern Miller, was taken before the samples carbon 14 testing were cut from the Shroud. It was taken with a heavily-filtered ultraviolet lighting (black light) that did not emit any visible light at all. All of the light you see in the photograph was produced by the fluorescence of chemical compounds on the Shroud. Any variations in color and brightness are a direct result of the chemical composition.

According to Ray Rogers:

I believe that this is one of the most important photographs of the Shroud that has been taken. It shows the fluorescence of the area of the radiocarbon sample. It proves that the radiocarbon sample did not have the same chemical composition as the rest of the cloth. This is a fact - not an interpretation. . .

Notice that the entire area above the Raes sample and along the seam is darker than the main part of the cloth. It does not fluoresce. . .Its chemical composition is different from the Shroud. That is exactly the area sampled for the 1988 dating fiasco. . .

The radiocarbon sample was invalid. No strange, magical events are needed to explain the invalid date. I do not know what the real date is, but I know the sample used in 1988 did not yield a valid date. The poor preparation for sampling in 1988, the poor verification of the sample, the failure to follow written protocols, and the unrealistic claims made about "unreliable" radiocarbon dating have done great damage.

Archeologists know well that carbon 14 testing is best suited for testing things that have been undisturbed and well protected from natural or manufactured contamination. Because of this problem and because unexplained anomalies in the measurements often occur, corroborating evidence of another kind is sought. For instance, an archeologist might try to compare the cloth with other linen examples from antiquity.

According to Methchild Flury-Lemberg, a leading authority on historic textiles and the former curator of Switzerland’s Abegg Foundation Textile Museum, it is similar to linen woven on Egyptian or Syrian tombs and used in Roman occupied Palestine. Flury-Lemberg reports that the Shroud resembles unique ancient textiles found in tombs of the Jewish palace-fortress Masada, reliably dated to between 40 BCE and 73 CE.

More significant is the fact that the yarn was bleached before the cloth was woven. This is not how linen was produced in Europe during the time in question. There and then, the entire linen was bleached after weaving. More ancient linen was manufactured as described by Pliny the Elder: individual hanks of yarn were bleached and dried before weaving. This produced batches of thread with slightly different off-white coloration.  With lighting from behind, X-ray-transmission, ultraviolet light and contrast-enhanced photography we can see discrete bands of yarn with different visual characteristics (x-ray densities and corresponding color densities).  Some areas show darker warp yarns and some show darker weft yarns.  In places bands of darker or lighter color cross producing plaid effect. Archeologically speaking, the cloth of the Shroud was not produced when the carbon 14 testing determined that it was.

 

Here is the issue: The outermost fibers of the cloth are coated with a thin film of starch fractions and saccharides. In places, bits of this coating have turned straw-yellow because of a chemical change. That is how the images are recorded, plain and simple. But it is not so simple. While heavy volatile amines coming from a body would have caused this chemical change (that is certain), it is puzzling that the images are focused and properly exposed. See:  The Hypothetical Shroud of Caiaphas

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Shroud of Turin Introduction  

© 2004 Daniel R. Porter, Bronxville, New York