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.
Abgar
Abgar V Ouchama, king of Edessa (ruled 13 – 50 CE) played a significant "legendary" role in the Shroud. Edessa was a cosmopolitan city in Jesus’ day and one of the cities were Christian communities developed early as they did in Antioch. Edessa, now the city of Urfa in modern day Turkey, is situated about 400 miles north of Jerusalem.
Historians have long known about an ancient cloth said to bear an image of Jesus known as the Image of Edessa, the Edessa Cloth, and later in the Byzantine era as the Holy Mandylion. We can be quite confident that this ancient cloth, which disappeared during the sacking of Constantinople in 1204 by knights of the Fourth Crusade, is the Shroud of Turin.
Legend has it that the cloth was brought to King Abgar V Ouchama of Edessa (13 – 50 CE) by one of Jesus’ disciples known to us as Thaddeus Jude (Addai). We know of this legend from Eusebius of Caesarea’s early fourth century Ecclesiastical History. Therein, we learn of a now lost document once in Edessa’s archives purportedly written by King Abgar V and delivered to Jesus by an envoy named Ananias. Abgar, supposedly, asked Jesus to come to Edessa and to cure him of leprosy. Eusebius’ history reports that the Apostle Thomas did send Thaddeus Jude sometime after Jesus’ death and that he founded a church in Edessa. Historians are highly critical of this legend since Eusebius’s history includes, as elements of the letter, references from the Gospels, which were written later, as well as theological concepts, which were developed later. It also must be pointed out that Eusebius makes no mention of the cloth.
Another Syrian manuscript, the Doctrine of Addai, fills in some gaps. According to this document, which also mentions the letter, Ananias painted a portrait of Jesus “with choice pigments.” A later document, the Acts of the Holy Apostle Thaddeus, written in the early part of the sixth century, adds more detail. It suggests that the image was formed when Jesus wiped his face on the linen cloth and it refers to the Edessa Cloth as a tetradiplon. We can only assume that this is all legend. But from this material we can gather three very important clues:
- The cloth arrived in Edessa.
- The image on the cloth is recognized to be unique in that the images were described as painted with choice pigments or formed when Jesus wiped his face on the linen cloth.
- The cloth is described as a tetradiplon, which means doubled in fours. When folded thus, only the face from the Shroud will be visible.
Regardless of how the image-bearing cloth arrived in Edessa, it was discovered in the early sixth century concealed behind some stones above one of the city gates. It was a practice in ancient cities of this area to mount a stone tile with a picture of some favored deity above the city’s main gate. It may be that the Image of Edessa was simply stored behind such a tile as suggested by some Byzantine iconography. It could well have been that because of severe floods, to which Edessa was very prone; the cloth was placed high in the city’s walls for protection. There is also the very real possibility that it was hidden to protect it from invaders or to protect it during times of Christian persecutions. We know that during the many persecutions of the first three centuries, valuable relics, writings, and ceremonial items of the church were routinely destroyed. There is evidence of local persecutions in Edessa as early as the latter part of the first century and of Roman persecutions that persisted until the time of Emperor Constantine. If, in fact, the cloth was taken to Edessa in the earlier part of the first century, it might have been hidden for protection as early as the reign of Ma’nu VI, Abgar’s son, who is thought to have reverted to paganism.
What is not legend, nor speculation, is that the cloth, with an image of what was then believed to be a true and miraculous facial image of Jesus – described as a divinely wrought image and an image not made by hand – was found in the walls of the city in the sixth century. During repairs of the city walls in 525 CE, or more likely, during a Persian invasion of the city in 544 CE, the cloth was rediscovered and placed in a church built especially for it. It was, to the people of Edessa, the lost cloth of the “legend.” In the late sixth century, Evagrius Scholasticus’ Ecclesiastical History mentions that Edessa was protected by a “divinely wrought portrait” (acheiropoietis) sent by Jesus to Abgar. In 730 CE, St. John Damascene in On Holy Images describes the cloth as a himation, which is translated as an oblong cloth or grave cloth. This may be the first mention, among extant documents, of it being a grave cloth.
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
Image Properties Observed Objectively by Scientific Methods
From Ray Rogers’ FAQ:
The image is extremely faint and difficult to see. Much more detail can be seen in contrast-enhanced and ultraviolet photographs; however, they are somewhat misleading to studies on image formation. Whatever produced the image color did not produce very much color. Scientific observations were planned in order to learn as much as possible about the image distribution and chemical composition.
The Shroud was observed by microscopy, visible and ultraviolet spectrometry, infrared spectrometry, x-ray fluorescence spectrometry, and thermography. Later observations were made by microchemistry, petrographic microscopy, scanning-electron microscopy, energydispersive x-ray analysis, pyrolysis-mass-spectrometry, and laser-microprobe Raman analyses.
Without making any assumptions that are based on the appearance of the image, some statements of fact can be proved from the scientific observations:
Reflectance spectra, chemical tests, laser-microprobe Raman spectra, pyrolysis mass spectrometry, and x-ray fluorescence all show that the image is not painted with any of the expected, historically-documented pigments and media.
No painting pigments or media scorched in image areas or were rendered water soluble at the time of the AD 1532 fire.
Direct microscopy showed that the image color resides only on the topmost fibers at the highest parts of the weave.
The color density of any specific image area depends on the batch of yarn that was used in its weave. The cloth shows bands of slightly different colors of yarn.
Adhesive-tape samples show that the image is a result of concentrations of yellow/brown fibers.
The image does not fluoresce under ultraviolet illumination.
The image of the dorsal side of the body shows the same color density and distribution as the ventral, and it does not penetrate the cloth any more deeply than the image of the ventral side of the body.
Thermography proved that the emittance of the image was the same in all areas. The entire image formed by the same mechanism. Spectra and photography confirmed this observation.
The only image color easily visible on the back side of the cloth is in the region of the hair. Fanti and Maggiolo were able to show traces of face and hand images by image processing.
No image formed under the blood stains.
The image-formation mechanism did not damage, denature, or char the blood. The blood can be removed with a proteolytic enzyme. The blood produced hydroxyproline at low temperatures in the pyrolysis/ms spectra. It was never heated significantly. Image formation had to be a low-temperature process.
Image color can be chemically reduced with diimide, leaving colorless cellulose fibers. All image color resides on the outer surfaces of the fibers.
The medullas of colored image fibers are not colored: The cellulose was not involved in color production.
The color of image fibers was often stripped off of their surfaces, leaving molds of the fibers in the adhesive. Growth nodes can be seen in the molds. The colored layers show all of the same chemical properties observed on intact image fibers (see 12 above). All of the color is on the surfaces of the fibers. The colored layer is 200-600 nanometers thick.
Chemical tests showed that there is no protein painting medium or protein-containing coating in image areas. The image was not painted with glair, and it follows that microbiological activity did not produce the image.
Microchemical tests with iodine detected the presence of starch impurities on the surfaces of linen fibers from the Shroud. An impurity layer could be seen by phase-contrast microscopy.
There is no evidence for tissue breakdown (formation of liquid decomposition products of a body). Body fluids (other than blood) did not percolate into the cloth.
Any radiation that is energetic enough or sufficiently intense to heat the cloth enough to cause the initial dehydration reactions of cellulose would penetrate into a fiber to a distance determined by its energy. Simple heating would change both the cellulose and blood. Both protons and neutrons leave characteristic tracks in flax fibers. The image fibers could not have been colored by energetic radiation.
Rapid heating, as when linen is scorched with a torch, leaves characteristic, small balls of solidified melt at the ends of fibers. No such features can be observed on the Shroud.
The cloth does not show any phosphorescence.
The blood on the cloth is still largely red. Old blood is normally black. Blood that has been hemolyzed remains red for a long time.
Neither aloes or myrrh could be detected on the cloth.
Optical and Physical Properties of Flax Fibers on Turin Shroud
From Ray Rogers’ FAQ:
Flax fibers look like small lengths of bamboo under a microscope.
The gross internal composition of a flax fiber is shown in the figure (after Cardamone).
The cellulose molecules in flax fibers are folded back and forth in a fairly regular arrangement, and they show the properties of crystallinity. The fibers are composed of closely packed "ultimate cells" of the fibrillar structure that are cemented together with holocellulose and lignin. You can see the ultimate cells under a microscope, and abraded fibers often show ultimate cells sticking away from the surface. These were the structures that were mistaken for "filamentous bacteria" by Garza-Valdes.
When you rotate the stage of a petrographic microscope with crossed polarizers while looking at a flax fiber, straight lengths change from black to colored every 45?. The fiber is birefringent and has an ordered structure. Most of the cellulose of the fibers is in a crystalline structure. In structures like flax, it is called a "fibrillar" structure.
McCrone ignored our agreements for work on the STURP sampling tapes: he stuck them all down to microscope slides. This made observations much harder; however, flax and cotton fibers can still be distinguished by their indexes of refraction.
Crystallographic observations must be made on the specific fibers that reach extinction at the same angle as the tape (while everything is black). The index of refraction of a normal linen fiber parallel to its length is nearly identical to that of the adhesive on the sampling tapes (it nearly disappears). That index is very close to 1.515. The index across the fiber is appreciably lower than the adhesive. The indexes of refraction and crystallinity of image fibers are identical to unaffected fibers. Bent, crushed, or otherwise damaged fibers show strain dichroism and will give an erroneous index. Most flax fibers show intense birefringence colors when they are viewed at a 45º angle from the plane of polarization of the microscope.
Cotton has a low birefringence, usually appearing white (first-order white), and it is a thin, wide tape that shows periodic reversals (twists).
Optical and Physical Properties of Flax Fibers on Turin Shroud
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.
Image Properties Observed Looking at 1532 Fire Damage to Shroud
From Ray Rogers’ FAQ:
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.
Image Properties Observed Looking at 1532 Fire Damage to Shroud
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
Why are Flax Fibers not Involved in Image Formation on Shroud of Turin
From Ray Rogers’ FAQ
Prof. Alan Adler of Western Connecticut University found that the image color could be reduced with a diimide reagent, leaving colorless, undamaged linen fibers behind. This confirmed spectral data that indicated that the image color was a result of complex conjugated double bonds; however, it proved that image color was found only on the outer surfaces of colored image fibers. Until this time, we had assumed that the image color was a result of chemical changes in the cellulose of the linen. The most likely change would involve the dehydration of the cellulose to produce conjugated-double-bond systems Adler’s observations proved that the cellulose was not involved in image formation. This is an extremely important observation.
This fact was confirmed by the observation that the image color on some fibers had been stripped off of their surfaces by the adhesive of the sampling tapes. The photomicrograph shows the places where two fibers were pulled out of the adhesive leaving their colored coating behind. The coating is too thin to measure accurately with a standard microscope; however, it appears to be 200-600 nanometers thick (in the range of a wavelength of visible light).
The bands of color and the fact that all of the image color appears only on the outer surfaces of the fibers, suggested that image formation involved a thin layer of impurities. Because the cellulose was not colored, the impurities had to be significantly less stable than cellulose.
This also suggested that the impurities were the result of cloth-production methods, and they should appear on all parts of the cloth. A search for carbohydrate impurities on the Shroud confirmed McCrone’s detection of some starch fractions. Starch and low-molecular-weight
carbohydrates from crude starch would color much more easily than would cellulose as a result of either thermal dehydration or chemical reactions.
Any image-formation mechanism that would result in color formation inside the linen fibers must be rejected. Some "theories" that have been mentioned that would cause coloration inside fibers are penetrating radiation, high temperature scorching (hot statue, painting with a torch, etc.), and catalyzed dehydration of the cellulose. Image fibers are colored only on their surfaces.
Flax Fibers not Involved in Image Formation on Shroud of Turin
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