Philip Ball on Thermochimica Acta Paper
Shortly after Rogers published his finding, in Thermochimica Acta, Philip Ball wrote an opinion piece for Nature, the journal that had published the carbon dating results in 1989. Ball wrote:
The scientific study of the Turin Shroud is like a microcosm of the scientific search for God. It does more to inflame any debate than settle it . . . . And yet, the shroud is a remarkable artifact, one of the few religious relics to have a justifiably mythical status. It is simply not known how the ghostly image of a serene, bearded man was made.
Ball’s assertion that it is not known how the image was made is correct. Scientists are not even close. There is no best explanation; not yet. There is no theory. Though there are some hypotheses, none seem to qualifies in terms of chemistry, physics and visual perception. The image remains inexplicable, baffling, downright weird. So far, even with the best of modern technology no one has been able to replicate it. We will explore it thoroughly. Its mysterious qualities are among the most entertaining and intriguing aspects of the shroud.
Skeptical Dictionary Position Softened
Robert Carroll’s Skeptics Dictionary has softened its once hardnosed refutation of the cloth’s authenticity since Thermochimica Acta published Rogers’ findings:
Of course, the cloth might be 3,000 or 2,000 years old, as Rogers speculates, but the image on the cloth could date from a much later period. No matter what date is correct for either the cloth or the image, the date cannot prove to any degree of reasonable probability that the cloth is the shroud Jesus was wrapped in and that the image is somehow miraculous. To believe that will always be a matter of faith, not scientific proof.
First off, Rogers did not speculate that it was 3,000 or 2,000 years old. What Rogers argued was that the lack of vanillin in the fabric of the shroud was a serious challenge to the carbon dating. Given a plausible range of average ambient temperatures during the life of the cloth, chemical kinetics demonstrates that the cloth is somewhere between 1,300 and 3,000 years old and not about 700 years old as the carbon dating suggested. Second, we need not ascribe miraculous causation to the image, as Carroll suggests, to infer at some level of certainty that it might be the shroud Jesus was wrapped in. There might be, as Rogers and other think, a perfectly natural chemical explanation for the images. The suggestion that the image might be from a much later period is interesting but improbable. One historical claim in support of such an idea, as we will see, doesn’t stand up to objective history or scientific analysis. Carroll perhaps is right when he states that the date cannot prove that the cloth was Jesus’ burial shroud. We need not cut off the debate, as Carroll does, by proclaiming that belief in its authenticity is simply a matter of faith. Yes, scientific proof might not be possible yet or ever, but a combined conspectus of history and science may be enough to infer that authenticity is the best explanation.
Can Bioplastic Polymer Coating on Shroud of Turin Explain the Carbon 14 Date
From Ray Rogers’ FAQ:
No. Stephen Mattingly of the University of Texas has proposed a hypothesis that a "bioplastic" coating on the Shroud produced an error in the 14C analysis that was used in obtaining the 1988 age estimate for the Shroud of Turin. He also proposed that common skin bacteria produced the image. I believe that there are several things wrong with these hypotheses.
Even assuming that the coating formed all at once in the 20th Century during a highfallout time, when bomb-produced 14C was high, an observable error in the age determination would require the addition of a significant amount of material to the surface of the Shroud. Mattingly proposes that the added material is a product of microbiological action. Such microbiological processes require fixed carbon, nitrogen, phosphate, sulfur, etc., to produce the products observed as biopolymers. The chemical components of biopolymers can be detected with great sensitivity.
Joan L. Rogers took authentic Shroud fibers, which she laboriously extracted from the STURP sampling tapes by washing them free of adhesive with xylene (not a solvent for any "bioplastic polymers"), to Metuchen, NJ, for laser-microprobe Raman analysis. The analysis is extremely sensitive, but nothing was observed that would indicate a "bioplastic polymer."
She also took fibers to the NSF Mass Spectrometry Center of Excellence at the University of Nebraska. They did pyrolysis-mass-spectrometry on the fibers. Their system was sufficiently sensitive to detect traces of the oligimers (low-molecular-weight polymers) from the polyethylene bag that Professor Luigi Gonella of Turin had used to wrap the Raes samples; however, the polyethylene never touched the samples. They were protected inside acid-free conservator’s paper.
The NSF facility observed the pyrolysis products of polysaccharides as a function of their relative temperatures of decomposition. For example, they detected traces of furfural from the anomalous pentosan gum layer in the radiocarbon-sample area. They easily detected hydroxyproline from the proteins of the blood spots. No evidence for a bioplastic polymer was detected on either non-image or image areas.
R. Rogers, J. Rogers, and A. Adler spent many hours looking at samples from the Shroud under microscopes and running microchemical spot tests. There were no anomalous indexes of refraction, there were no amorphous materials cementing fibers (except for the blood/serum and some pentosans on yarn segments taken from the Raes and radiocarbon samples), and there were no sulfur compounds on the surface (except in the blood/serum areas). No "bioplastic polymers" are absolutely devoid of amino acids (proteins) and sulfoproteins. There is no significant amount of bioplastic polymers on the main part of the Shroud.
In order to change the carbon date, the organisms Mattingly postulates must be utilizing carbon dioxide from the atmosphere. A 14N n-p 14C nuclear reaction in the upper atmosphere is the source for 14C-containing carbon. The addition of modern carbon is the only way to decrease the apparent age of ancient carbon-containing material. The organisms that fix CO2 are photosynthetic, and they are "obligate aerobes." They must have oxygen in their atmosphere as well as CO2. They need a source of energy. They get that energy by absorbing light into complex colored molecules that then provide electrons for the chemical reactions that involve the carbon and other reactants. The final products of photosynthesis are sugars, polysaccharides, nucleic acids, proteins, etc. Nature builds flax (linen), trees, grass, and little colored microorganisms by photosynthesis. All of the 14C in our bodies comes originally from photosynthetic organisms. The most important organisms that fix CO2 are plants, mostly green plants.
Mattingly’s postulation of an appreciable amount of slime/biopolymer requires photosynthetic aerobes. They all use water, CO2, and light, and they produce fixed carbon and oxygen. The oxygen we breathe comes from photosynthesis. Appreciable photosynthesis would not be expected on the Shroud, because historically it was stored dry in a dark place.
All photosynthetic organisms contain intensely colored pigments, for example chlorophyll. All such pigments absorb visible light and reflect intense colors. They all show distinctive spectra. Some of the most important observations made by STURP in 1978 were the reflectance spectra of the image, blood, and non-image areas of the Shroud. We could not have missed any pigments that are involved in photosynthesis.
If the organisms involved in biopolymer production (like fungi) used only the carbohydrates in the Shroud for their metabolic purposes (we call it "rotting") and did not fix atmospheric carbon by using pigments, the biopolymer product would show the same carbon age as the Shroud. Such effects have been observed. The organisms would use fixed carbon (e.g., the sugar units of cellulose) and yield carbon dioxide and cell components. Only part of the metabolized carbon would end up in a slime/polymer layer, and the cloth would tend to disappear much faster than the polymer appeared.
All biopolymers are products of living organisms. They contain proteins, amino acids, and nucleic acids. Algal cells contain 3.9% nitrogen and 3.3% phosphorus. Fungal cells contain about 0.9% phosphorus and 2.9% nitrogen. Compounds containing these elements can be detected by several of the analytical methods STURP used. The polymers can be nearly pure polysaccharides, but they all give protein spot tests.
STURP used all of the protein spot tests, e.g., Hycel biuret followed by Fisher Folin reagent, biuret Lowrey, amido black, iodine-azide to look for sulfoproteins, and a sensitive pyrolysis test that detects the purine from proteins. There was no protein in areas other than the blood flows. There was no bioplastic-polymer coating.
Mattingly and Garza-Valdes presented a photomicrograph of a linen fiber from the radiocarbon sample. It shows a thick coating and what are indicated to be "filamentous bacteria, a snake-like growth." They did no analyses to support their claims, and they apparently know nothing about the structure of linen. Features identical to the "filamentous bacteria" are common in linen samples. They are what are called "ultimate cells."
Linen fibers are made of parallel bundles of these cells, cemented together with lignin and hemicelluloses. Details can be found in a paper presented by Jeanette Cardamone ["The Turin Shroud Past, Present and Future," International Shroud Scientific Symposium (Torino 2-5 March 2000)]. There are images of flax fibers, drawings, and text explanations. She has said that: "Any fuzziness could be due to abrasion that causes micro-fibers to develop on the surface of the fiber and, critically, remain attached to it." In other words, things that look like filamentous bacteria are to be expected on linen fibers.
Ultimate cells are easy to differentiate from bacteria, because the ultimate cells are crystalline and birefringent. It is too bad that the "bioplastic-polymer" proponents did not do any analyses of their samples. They have caused massive confusion and mischief.
A good discussion of this problem was presented by Harry Gove in the paper that presented the bioplastic-polymer hypothesis [Gove, Mattingly, David, and Garza-Valdes, Nuc. Inst. and Methods in Physics Res. B, 123 (1997) 504-507].
It would be important to know when the contamination appeared in order to know how much effect it would have on the date. Obviously, if all of the contamination occurred in about AD 33, there would be no change in the apparent age. If all of the contamination appeared at the time of the fire of 1532, 79% of the carbon in the Shroud would have to have been from the contamination and only 21 % from the original cloth in order to give a date of 1357.
This problem applies to all postulated types, amounts, and ages of possible contamination. Contamination had little or no effect on the age reported by Damon et al.
Bioplastic Polymer Coating on Shroud of Turin and Carbon 14 Date
Future Scientific Study Options Following 2002 Restoration
From Ray Rogers’ FAQ: (Answer for this question is the same as for The 1532 fire and image properties, as published)
Although the fire of 1532 nearly destroyed the Shroud, it created opportunities for many types of chemical studies. We would never use the same destructive methods of observation on an undamaged relic, but misadventure gave us many unexpected options. The important fact is that, before the restoration, we could look at the chemistry of specific locations on the Shroud where scorches intersected image, blood, serum, and water stains. The restoration destroyed much chemical information at those intersections.
If the image had been painted or retouched, some foreign materials had to be added to the cloth. The pigments and vehicles (e.g., the ochers, realgar, orpiment, mosaic gold, glair, gums, and glues) would have been subjected to a violent "chemical test" during the fire. The temperatures, temperature gradients, pyrolysis products, and water used to extinguish the fire would have changed the chemical composition of most foreign materials. Before going to Turin in 1978, we did many experiments on the stability of the painting materials. We had hoped that future observations on the Shroud could compare predictions with reality. The restoration disturbed exactly the areas of most chemical importance.
The persons involved in the restoration of June and July 2002 did not appear to be familiar with previous scientific observations, and they did not consult chemists with different areas of experience or chemically-oriented textile conservators. The restoration destroyed much of the chemical information that could have been recovered as a function of position on the surface of the Shroud.
The fire of 1532 produced many extremely reactive pyrolysis products, and the fire was extinguished with water. All paints that were used during or before medieval times (except gold) are changed by heat and/or the chemically reducing and reactive pyrolysis products of the cloth (e.g., formaldehyde, furfural, organic acids, CO, etc.). For example, red hematite would have been reduced to black magnetite. This fact provided one basis for refuting McCrone’s claim that the image was painted with hematite. We planned to look for the products of such reactions. Some medieval painting materials become water soluble, and they would have moved with the water. A huge amount of chemical information existed in the scorches.
Most organic colors are much less stable than cellulose (linen) and the normal inorganic pigments. Experiments in 1978 showed that scorch lines in impurities precede the scorches in pure linen. Most organic materials, including natural products, change in predictable ways in response to heating and the known products of cellulose pyrolysis. We even tested squid ink, which had been reported being used in ancient times.
It might still be possible to extract the products of the reactions from the materials recovered during the restoration, assuming that samples were segregated and locations were recorded. Such information could be important for suggesting the chemical composition of the image. Most possibilities for directly studying the effects of the fire on image materials were destroyed by the restoration of 2002.
Visual and microscopic observations on the Shroud in 1978 indicated that image color or its reaction products did not move with the water. Other unidentified products did move. Aldo Guerreschi has suggested that two different sets of water stains exist on the Shroud. They could contain interesting chemical and historical information. We had counted on the tape samples and possible future direct studies on the scorch/water-stain areas of the Shroud for detailed chemical confirmation of what did and did not move with the water. Now the tape samples are kept from scientific study by the officials in Turin, and scorches were destroyed by the "restoration."
The Shroud showed many locations where scorches of different severity intersected image and/or blood. Thermal gradients can be estimated on the basis of scorch colors. Temperatures are the most important factors in calculating chemical rates. We made predictions on the kinds of products that might appear in image areas as a result of reactions between its components and the pyrolysis products and water. These predictions could be used to test many of the hypotheses that have been proposed for image formation.
I took samples from many scorch/water/image intersections in 1978, but observations on them generated more questions. Answers required additional observations and/or samples. The samples are now secreted in Turin. As a result of the restoration, any future studies will be much more difficult and expensive: Some will be impossible.
The Shroud is a structure composed of chemical compounds, and all of the main ones have been studied in detail. They are published in chemical text books. Chemical analyses can yield considerable definitive historical information. All manipulations of the Shroud should be considered in detail in order to preserve as much information as possible.
Linen-production technology has changed through the centuries. We have assembled chemical information related to the technology, and we have consulted textile experts who have done detailed chemical research that relates to the composition of the Shroud. Our detailed analyses suggested that the cloth had been prepared by technology common before about AD 1200. It best resembles linen made in the Near East during Roman times. These results do not agree with the date published in 1989. The differences can be explained on the basis of samples from the radiocarbon area, but all scientific observations should be confirmed. Samples from the restoration might help confirm the properties of the radiocarbon sample; however, the persons involved in the restoration fight any attempt to test and confirm the truth. No scientist in Torino will discuss the problem, and the custodians refuse to recognize the problem. Ethical science is impossible in such an environment.
Lignin is a structural polymer that is found in all plants, including flax. Linen is bleached in an effort to remove as much lignin as possible, but some lignin always remains in linen. Lignin slowly ages with the loss of vanillin (4-hydroxy-2-methoxybenzaldehyde). A very sensitive microchemical test exists for the detection of traces of vanillin. It is easy to detect vanillin in modern lignin, it is harder to find in Medieval linen, and no test can be obtained from the few Shroud fibers that are still available for study. The lignin in samples from the Dead Sea scrolls (ca. AD 70) does not give the vanillin test. This observation would suggest that the linen of the Shroud is very old, casting doubt on the accuracy of the 1988 date. Observations on the lignin could be confirmed with samples from the "restoration"; however, such samples are jealously guarded in Turin.
The tape samples show that much of the charred material is elemental carbon. It is very inert chemically. It would not have changed during the 470 years since the fire. Published concerns about isotope fractionation during the fire are nonsense. The carbonized material can easily be chemically cleaned of any organic deposits that might have appeared after the fire, making it an ideal material for radiocarbon dating. Before the restoration, the carbon from specific areas could have been dated separately, giving critical information about the homogeneity of the cloth as well as "clusters" of dates. Clusters of dates are more reliable than dates on single samples.
Dr. Max Frei took tape samples to recover pollen grains from the surface of the Shroud in 1973 and 1978. Sweeping claims have been made on the basis of Frei’s samples, but published photomicrographs do not support the claims. Other reports suggest that there were major changes in the number of grains found on Frei’s tapes between the time of his death and more recent publications. The pollen data badly need confirmation. The restoration totally destroyed any chance to take valid additional pollen-grain samples from the surface of the Shroud. A suspicious person might wonder whether the "restoration" was rushed through to prevent ethical work on confirming both chemical and pollen observations.
Biblical accounts suggested several types of compounds that might have appeared on the cloth (e.g., aloes, myrrh, sebaceous secretions, etc.). We planned and executed chemical analytical methods that could detect them in 1978. Those methods were extremely sensitive, but they did not detect squalene or myrrh. These results could have been confirmed by additional tests on the Shroud, but the "restoration" has totally changed the Shroud’s surface.
The surface of the Shroud could have been analyzed by Electron Spectroscopy for Chemical Analysis (ESCA), which observes the top few nanometers of the surface. Now that the surface has been disturbed, that powerful technique will be much more difficult to apply, and results will be ambiguous. This is a terrible, discouraging loss for Shroud chemists.
The problems associated with surface analyses are now compounded by the fact that thymol was used to sterilize the reliquary after the 1988 sampling operation. Thymol is a phenolic compound that will react with many functional groups on the Shroud. This will confuse image analyses, and it may result in damage to the cloth. As one example, we found a significant amount of iron in the Shroud’s cloth. Iron reacts with phenolic compounds to form complexes, and some of them are intensely colored. I would urge the custodians of the Shroud to consult with chemists before taking other irreversible actions.
One justification for the hurried, secretive restoration was a fear of "autocatalytic" degradation of the cloth. No experts on chemical kinetics were consulted. The Shroud has not been and is not now in danger of autocatalytic degradation (see FAQ 6).
Chemical autocatalysis is responsible for the destruction of books that are made with cheap, acid paper. Claiming analogy with the Shroud is mischievous. Adler and Schwalbe made the following comment: "Previous chemical reactions on the cloth, e.g., the retting process in manufacture of the linen, the known historic fire and its extinguishment, and previous display and storage procedures, have left a variety of chemical structures on the surface that can act as oxidants and also as catalysts. For example, the acidic structures produced by previous oxidative activity can strongly promote various types of autocatalysis" [A. D. Adler and L. A. Schwalbe, "Conservation of the Shroud of Turin," Shroud Spectrum International, No. 42, December 1993, Indiana Center for Shroud Studies]. Such claims led to the secret restoration. Secrecy is never productive, and the plans for a restoration should have been reviewed with as large a group of scientists as possible. The restoration was a terrible mistake.
Other Ways than Radiocarbon to Date Shroud of Turin-Carbon 14
From Ray Rogers’ FAQ:
Archaeologists use many different methods to estimate the age of artifacts and/or soil strata that contain artifacts. One of the most important ways is to observe changes in technology: methods used to make tools change with time. There is a big difference between the hand axes made during the Paleolithic and fine arrow points made a few hundred years ago. The technology used to make the Shroud was much different than that used during medieval times or modern times.
Stone tools hydrate and form a patina. Its thickness indicates age. Similarly, all organic materials tend to decompose or change structure with time. Proteins undergo "racemization." Their amino acids change their optical properties. This would apply to the blood on the Shroud.
The DNA in blood and tissue samples degrades with time. The DNA in Shroud blood samples shows the effects of significant aging: only short lengths of the chain remain intact. The reported ABO typing results are very suspect and probably not valid. However, the results prove appreciable age for the Shroud.
Crystalline materials undergo damage that is caused by natural sources of radiation, and Shroud fibers show some evidence for changes in their crystal structure.
Some compounds like lignin change composition with time. The lignin in the Shroud does not give the normal microchemical test for vanillin, indicating that it is quite old. Measurements of the chemical rate for loss of vanillin estimates an age for the Shroud of more than 1300 years, depending on storage conditions.
Other Ways than Radiocarbon to Date Shroud of Turin-Carbon 14
How do you know that the radiocarbon sample was not valid for dating the Shroud of Turin?
From Ray Rogers’ FAQ
The 1988 radiocarbon age determinations were carefully done. The sample preparation methods, the measurement technologies and procedures, and the data reduction were adequately planned and executed to answer the most important question: was the Shroud produced in the First Century? Damon, et al., reported that "The age of the shroud is obtained as AD 1260-1390, with at least 95% confidence." However, that date does not reflect observations on the linen production technology nor the chemistry of fibers obtained directly from the main part of the shroud in 1978. The independent analyses from the different laboratories scatter more than would be expected for a homogeneous sample, raising other questions.
The 1988 sampling operation was described as follows: "The shroud was separated from the backing cloth along its bottom left-hand edge and a strip (~10 mm x 70 mm) was cut from just above the place where a sample was previously removed in 1973 for examination. The strip came from a single site on the main body of the shroud away from any patches or charred areas." The use of a single sample, assuming it was representative of the whole cloth, defied normal procedures and protocols established before the radiocarbon study. It was a serious mistake.
To make matters worse, Mssrs. Franco Testore, professor of textile technology at the Turin Polytechnic, and Gabriel Vial, curator of the Ancient Textile Museum, Lyon, France, approved the location of the radiocarbon sample without any serious attempt at characterizing the sample. No chemical or careful microscopic sample characterizations were made. The 1988 work did not guarantee the validity of the sample.
The area where the radiocarbon sample was obtained had been photographed in 1978 with an ultraviolet source (see "UV fluorescence"). While making the UV photographs, the source was heavily filtered to exclude visible light and the camera was heavily filtered to exclude any effect of the UV on the film. All that appears on the film is the result of pure fluorescence. All fluorescence is a result of the chemical composition of the material.
The non-image cloth typically shows weak fluorescence (upper right). When image appears on the cloth, it quenches the fluorescence and gives it a brown color (see "Hands" below). The small, triangular, white area is where the Raes sample was cut in 1973. The radiocarbon sample was cut upward from there about 1 cm to the right of the seam and about 7 cm long. The area where the radiocarbon sample was taken is relatively dark, a fact that is not the result of dirt, image color, or scorching. The cloth is much less fluorescent in that area, brightening into more typical fluorescence to the right. The photograph proves that the radiocarbon area has a different chemical composition than the main part of the cloth. This was obviously not considered before the sample was cut.
Raes and radiocarbon yarn show colored encrustations on their surfaces. Some sections of medulla contain some of the material, showing that it had been able to flow by capillary attraction as a liquid. The encrustation is not removed by nonpolar solvents, but it swells and dissolves in water.
There was absolutely no encrustation on either the Holland cloth or fibers from the main part of the Shroud.
Al Adler had found large amounts of aluminum in yarn segments from the radiocarbon sample, up to 2%, by energy-dispersive x-ray analysis. I found that the radiocarbon sample was uniquely coated with a plant gum (probably gum Arabic), a hydrous aluminum oxide mordant (the aluminum found by Adler), and Madder root dye (alizarin and purpurin). Nothing similar exists on any other part of the Shroud. The photomicrograph shows several fibers from the center of the radiocarbon sample in water. The gum is swelling and slowly detaching from the fibers. Many red alizarin/mordant lakes can be seen, and yellow dye is in solution in the gum. Several cotton fibers are visible, a situation unique to the Raes and radiocarbon samples.
The radiocarbon sampling area had been dyed to match the old part of the cloth. The sample chosen for dating was totally invalid for determining the true age of the Shroud.
Radiocarbon C14 Sample Not Valid for Dating the Shroud of Turin
Raymond Rogers to the Editor of Skeptical Inquirer
Letter from Ray Rogers to the editor of Skeptical Inquirer:
I accepted the radiocarbon results, and I believed that the "invisible reweave" claim was highly improbable. I used my samples to test it. One of the greatest embarrassments a scientist can face is to have to agree with the lunatic fringe. . . . Joe [Nickell] did not understand the method or importance of the results of the pyrolysis/mass spectrometry analyses, and I doubt that he understands the fundamental science behind either visible/ultraviolet spectrometry or fluorescence. He certainly does not understand chemical kinetics. If he wants to argue my results, I suggest that we stick to observations, natural laws, and facts. I am a skeptic by nature, but I believe all skeptics should be held to the same ethical and scientific standards we require of others.
What was Teddy Hall’s Famous Quote on the Shroud of Turin
“We have shown the shroud to be a fake. Anyone who disagrees with us ought to belong to the Flat Earth Society.”
Teddy Hall, the director of Oxford’s Research Laboratory for Archaeology and the History of Art , following carbon dating of the Shroud of Turin in 1988. (Source: Alan D. Whanger, Professor Emeritus, Duke University Medical Center)
Was it justified? Possibly, assuming that carbon dating is the absolute final answer. It was no longer justified one it was decisively shown that the carbon dating was invalid.
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