Chemistry
Garlaschelli’s Shroud
In October of 2009, Luigi Garlaschelli, a professor of organic chemistry at the University of Pavia in Italy, created an image that looked a lot like the Shroud. It was a combination of body rubbing and bas-relief rubbing using a pigment laced with acid. The acid formed an etched image in the cloth’s fibers that became noticeable after the pigment was washed away. However, it too, failed to reproduce the complex image on the Shroud. Nonetheless, in each instance, the media reported that the Shroud had finally been reproduced. They failed to note that they had previously reported the same thing. They repeated the story line that until now no one had been able to explain how the images might have been formed. Rebuttal to these claims, no matter how scientifically or logically justified, got scant attention.
When Garlaschelli’s attempt was reported in the press, a mild explosion happened in a corner of the Internet. In blogs, chat rooms and Twitter tweets, skeptics and proponents of authenticity verbally slugged it out for a few days. Fans of each attempt to explain how a forger did it surfaced, but not so much to defend a favorite theory but to disprove all the other theories. They succeeded admirably. It resembled a circular firing squad; no one was left standing. But bloggers, like cats and monsters in video games, have many lives. We can expect the same thing the next time someone shows how a forger created the images.
Skeptics
DictionaryEach attempt to reproduce the images presumed that the carbon dating was correct. When it became obvious, to some, that the cloth was very much older, some skeptics modified their stance. Robert Carroll, in his popular, thorough and well written Skeptics Dictionary, wrote, “Of course, the cloth might be 3,000 or 2,000 years old . . . but the image on the cloth could date from a much later period. (1)
Wilson commented along the same lines, “However, it [new evidence about the age of the cloth] doesn't impact my theory much at all. A handy place for some profiteering villain to grab a good burial shroud for purposes of forgery, is from a tomb in Palestine. . . . a BC date won't necessarily toss the Shadow Theory.” (2)
Others were seemingly unaware that serious research was being published in the recondite, specialized, peer-reviewed journals of science; articles that proved that the carbon dating was invalid and articles that characterized the chemistry and physical attributes of the images.
Molly from Alaska
This unawareness was underscored for me when one day, in 2005, I received an email from Molly, a high school student in Alaska. Her chemistry teacher had handed out a sheet of paper with the title, “Carbon 14 Dating Successes.” It was a list and the topmost item read, “Shroud of Turin proven fake.” She had questioned the accuracy of the two words, proven fake.
“I asked my teacher about it,” she wrote, “but was ridiculed for not being scientific.” In front of the entire class her teacher said that she could believe anything she wants about her religion, but when it comes to science, the shroud is a fake. It was, he had said, a scientific fact.
For a class examination, she had to agree that the shroud was fake or be marked down. She objected. She brought to class an article from Wikipedia, the controversial online, community-edited encyclopedia banned by many teachers because of its sometimes questionable reliability. But, she also brought an article from the New York Times and another one from BBC News. They all said the same thing: There were substantive reasons to doubt the 1988 carbon dating results. She was looking for a copy of an article from a peer-reviewed scientific journal that had been mentioned in the news articles. Did I have a copy? I did, and I sent it to her.
Benford and Marino Onto Something
As it turned out, Benford and Marino seemed to be onto something. In 2002, after considerable research, Rogers, along with Anna Arnoldi, a chemistry professor at the University of Milan, wrote a paper that strongly suggested that Benford and Marino were right. More work needed to be done, however, and Rogers continued to study the matter with material that had been saved from the actual cuttings from which the carbon dating samples were taken. In January, 2005, following a lengthy peer-review process, Thermochimica Acta, an international journal from Elsevier, the world’s largest publisher of scientific journals, published a paper by Rogers entitled, “Studies on the Radiocarbon Sample from the Shroud of Turin.” In it Rogers wrote:
The combined evidence from chemical kinetics, analytical chemistry, cotton content, and pyrolysis/ms proves that the material from the radiocarbon area of the shroud is significantly different from that of the main cloth. The radiocarbon sample was thus not part of the original cloth and is invalid for determining the age of the shroud.
This wasn’t religious opinion. In fact, it wasn’t that much of a scientific opinion of the sort that newspapers and television like. If Rogers could have proven that the shroud was the genuine article or at least that it came from the time of Christ, this would have been exciting news. As it was he was only saying, that for all practical purposes, the 1988 carbon dating was meaningless. It was pure science. It was also a personal admission that he had been wrong in thinking that the carbon dating was the end of the story; that the shroud was certainly a medieval fake.
The Shroud of Many Myths
Shortly after Rogers published his finding, in Thermochimica Acta, Philip Ball wrote an opinion piece for Nature, the same 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. (4)
Ball’s assertion that it is not known how the image was made echoes what so many repeatedly say over and over. It isn’t just those who try to prove the shroud is fake by creating look-a-like images. Scientists who think the shroud might be real—or not—don’t know how the images were made. They are not even close. There is no best explanation; not yet. There is no theory. Though there are some guesses, some hypotheses, none seem to qualify in terms of chemistry and physical characteristics. The images remain inexplicable, baffling, downright weird. Forget about how some medieval forger might have made the images. Even with the best of modern technology no one has been able to replicate them. That doesn’t mean they won’t. It may just be a matter of time and new ideas. It is a challenge. The mysterious qualities found in the images are among the most intriguing aspects of the shroud.
Walter McCrone
One the flip side of the authenticity debate is the claim that one scientist, the late Walter McCrone (1916-2002), found red ochre (hematite) and vermilion (mercuric sulfide), common medieval paint pigments, and thus was able to argue that the shroud was painted. But that claim has since been proven wrong. Scientists—and we should probably only consider those who have actually looked at shroud fibers with microscopes and advanced scientific instruments—are quite certain about the chemistry of the images, and they are not made up of inorganic compounds McCrone identified through the lens of his microscope. The images are the result of a chemical change either to the fibers themselves or to some organic material on the fibers that was there before the images were made.
An analogy is in order. If you have a personal computer, you probably have an inkjet printer attached to it. When you print a picture, tiny droplets of ink are deposited onto the paper through tiny nozzles in a print head that passes over the paper. This is applied color. But it doesn’t really matter how color is applied with a paint brush, a pallet knife, drizzled on as Jackson Pollock did on his canvasses, powdered on as makeup is sometimes applied, or ink-jetted on. And it doesn’t matter if the colorant is paint, lipstick, dye or ink. The operational word is applied.
But there different types of printers that are inkless. Images are formed by a color producing chemical change to the media or to a coating on the media. One common type of inkless printer is a thermal printer. Thermal printers are often found in ATMs, cash registers and older fax machines. Paper that is coated with thermal sensitive chemical passes under a print head that heats tiny regions of the paper resulting in a chemical change that is evident by the change of color. This is not to imply that the images on the shroud were produced by heat. Many things can cause a color producing chemical change including other chemicals. Old newspapers that have become yellow, leaf stains on concrete, rust, these are all examples of color producing chemical changes.
Academies of Science
These people were important. Bacon’s expansion of the Alhazen’s scientific method and William of Ockham’s parsimony, which has become something of a creed in science known as Occam’s Razor are examples. But science in the modern sense, depended less on any individual as it did with organization. London’s Invisible College, a confederation of natural philosophers that became the Royal Society of London for the Improvement of Natural Knowledge in 1660 was the first of these. Newton, Darwin and Lyell would become some of its most famous Fellows. Today, it is simply known as the Royal Society. It is the scientific academy of the United Kingdom and the British Commonwealth. To be elected to membership is one of the greatest honors a scientist can receive.
The formation if the Académie des sciences in Paris in 1666 was next. Other nations and major cities followed suit. The Royal Swedish Academy of Sciences was founded in 1739. It is best known for every year selecting the Nobel prize winners in chemistry and physics. In 1863, the United States National Academy of Science was formed when President Abraham Lincoln signed it into being. Today most countries, many states and large cities have honorific science academies and societies.
The Medically Accurate Images
The ever so medically accurate images have convinced many people that the shroud cannot be a forgery. There are just too many details to reasonably imagine that a medieval forger, without a modern knowledge of forensic pathology could have created the shroud images including the bloodstains, unless, as Crossan supposes, he had an actual victim. But it had to be more than a victim to use as a model because some of the details are invisible without modern technology. Fred Zugibe tells us:
Under ultraviolet fluorescent photography, all of the wounds show a serum retraction ring of albumin around them that would have been completely unknown to an artist forger. It is very important to note that no image is present wherever blood is present, indicating that the image formation occurred after the blood staining and that the presence of blood prevented image formation in those areas. Although this is not discernable with. the naked eye, this was demonstrated by Adler [Professor Emeritus at Western Connecticut State University and one of the world’s leading authorities on the chemistry of blood] who removed blood from several fibers in image areas by subjecting them to proteolytic enzymatic hydrolysis (which removes blood). No image was present on the fibers that contained blood. If this were done by human hands, the artist would have had to paint all of the bloodstains with the albumin halos in all of the wounds and blood flows, including the blood of the scourge marks, using human blood and then paint the body image around them in their precise locations and eliminate images wherever there was blood. A complicated process, indeed.
Several forensic pathologists have examined the details of the images and the peer-reviewed papers in scientific journals. The conclusions are always the same. This is the image of a man who died of crucifixion, who is in a medically accurate state of rigor mortis, with medically precise wounds. The images are far too accurate to have been the product of anyone with only a medieval knowledge of anatomy or medicine. The blood is real human blood and it could only have come to be on the cloth by contact with real wounds.
Have We Missed Something?
Have we missed something else? Is there something on the shroud that is in Turin that we didn’t notice, or that was so small we could not readily see it, or something so bound up in the cloth’s chemistry that we could not even see it with an ordinary microscope? Might we find in these things something that might corroborate the gold nuggets of history so far? Might we at least find something that shows us that the cloth might indeed be old enough to have been in Constantinople, Edessa before that, and maybe Jerusalem before that?
Mathew Brady
During the American Civil War, using a process very much like one proposed by Herschel, Mathew Brady became the most famous photographer of the 19th century. He amassed a collection of photographic glass plates that numbered 10,000. Often unrealized is the fact that most of Brady’s photographs were not taken by Brady. He employed many photographers and purchased negatives from others. But when displayed or printed they all contained the obligatory caption, “Photograph by Brady.” It was a slight-of-hand. He provided the pictures. He was misunderstood.
It should not be thought that the invention of photography that brought it to its current state of development in 1898 rested mainly on the shoulders of Niépce, Daguerre, Talbot and Herschel. They stood on the shoulders of others who learned many things about chemistry. Wilhelm Homberg, is an example. In 1694 he explained how some chemicals darkened when exposed to light.
By 1898 photography was on the boundary between the old and the new. The old was large cameras with a front that held a lens, a back that held glass plates to be exposed, a bellows in between. The new was celluloid film developed in the 1880s and hand held cameras in the 1890s. In 1898, Kodak introduced a folding pocket camera.
Modern Biblical Literalism in Pia’s Day
In 1898, modern biblical literalism, particularly as it is seen in North America, had not yet emerged. That would happen in the next decade, in the years leading up to World War I, as a response to the liberal interpretations emerging from the Quest for the Historical Jesus, Darwinism and modernity in general.
The situation was different in France, particularly in the Académie des Sciences. It was perceived to be, if not the high temple of Atheism and Agnosticism, at least a precinct where the mention of God or Christ was off limits. This is probably not surprising given France’s strong secular attitudes born of the French Revolution.
Delage, amongst his French colleagues, had committed a heresy. Marcelin Berthelot, the secretary of the physics section of the Academy, the renowned discoverer of thermo-chemistry principles, and a militant atheist, ordered Delage to rewrite his paper so that it dealt only on the chemistry and made no mention of Christ. One can’t help but think of Galileo being told to retract his conclusions. His conclusion was omitted from official published proceedings. It was silly. It was akin to an ostrich hiding its head in the sand—which we all know they don’t do as we realize it wouldn’t work well. Newspaper reporters had the story and the Paris edition of New York Herald trumpeted the headline, "Photographs of Christ's Body found by science."
The Real Issue
The issue was not the chemistry. It was not a problem that an image of a man was perhaps formed by vaporous action and chemical reaction. The issue was perhaps not even that the body might be a crucified man. The issue was the notion that for the cloth to have survived at all, it required that the man and the cloth be separated before purification destroyed the image and ultimately the cloth. The implication that it was so was because it was Christ’s burial shroud and because it was Christ’s burial cloth it was as it was.
It lighted a torch that has remained lit since the day that Pia took his picture and Delage pronounced his conclusion.
Because the image on the cloth itself is a negative image, and because we can’t figure out any other way that might have come about short of a miracle, we might be tempted to think that a forger of relics figured out how to make a really big photograph. If we are still wedded to the idea that it must be medieval—rejecting the possible history and not being informed about the problems in the carbon dating—we need to come up with a new inventor of photographic negatives, someone other than William Fox Talbot to whom historians usually give the credit.
Leonard da Vinci Fooling Us All?
In How Leonard da Vinci Fooled History we learn that he secretly invented photography and then created a gigantic camera obscura, discovered how to make film out of linen, how to develop the picture and fix it. He was a genius, after all, they remind us. He understood the camera obscura (as had many educated people in Alhazen’s day and since). He had experimented with chemistry (as had many educated people). He might have had a motive. The authors on their website tell us he was, “[a] known joker, conjuror and illusionist, and a Church-hating heretic.”
A big problem for Picknett and Prince was the fact that Leonardo was born a century after the shroud was exhibited in Lirey. It was therefore necessary that he have an opportunity to replace that shroud with the one of his own making. He might have been welcome at the Savoy family palace. After all they had one of his drawings. “he had the means, opportunity and motive to create this extraordinary work.” Not only did he do all these things, dabbing on blood in all the right places, he replaced the head of the crucifixion model with a photograph of his own head. Picknett and Prince figured this out by comparing the head to a drawing of Leonardo and found the eyes and the nose and the mouth were all in the same place.
Why Not!
Alan D. Adler, Emeritus Professor of Chemistry at Western Connecticut University, in an article, “The Nature of the Body Images on the Shroud of Turin,” commented on those advancing this theory:
[they] propose a photochemical mechanism with sunlight reflected from a statue via optics to image on sheet of cloth charged with a mixture of egg white and chromium salts. As this is an albedo image, it will fail a VP-8 test and there is no chemical or spectroscopic evidence for their chemical sensitizers. They do not deal with the blood image problem [“exudates from clotted wounds transferred to the cloth by its being in contact with a wounded human male body”]. Leonardo may rest easily in his grave. (40)
Hair Color Has Nothing to do with Light
The reason that the hair appears blond in the images may have nothing to do with ethnicity and everything to do with chemistry. Rogers has suggested:
I believe that the most important effect of the hair was to impede the diffusion of gases (vapors). This would concentrate them in the area of the hair. More would diffuse through the cloth in that area. A higher concentration of vapors from the nose and mouth would appear on the back side of the cloth in back of the hair. I still believe that diffusion of gases can explain many of the observations on the image and its chemistry.
The idea that the man of the shroud looks European is highly subjective. Take a few minutes to read skeptical accounts on the Internet and you will see over and over that it the gaunt appearance, combined with the whitish hair that conveys that impression. You will also read statements like, “I read that Leonardo da Vinci photographed it,” or “I heard it has been proven to be a painting,” or “carbon dating proved it’s a fake,” or “linen is biodegradable and can’t last 2000 years.” I suppose linen found with the Dead Sea Scroll or the wrappings of mummies from 4500 years ago don’t count. But the indo-European appearance resonates with many people. But does appearance equate to reality?
Biggest Carbon Dating Mistake
There is a lot of other evidence that suggests to many that the shroud
is older than the radiocarbon dates allow, and so further research is certainly
needed. Only by doing this will people be able to arrive at a coherent history
of the shroud which takes into account and explains all of the available scientific
and historical information.
- Christopher Ramsey, head of the Oxford Radiocarbon Accelerator Unit which participated in the 1988 Carbon 14 Dating of the Shroud. (March 2008)
[T]he age-dating process [in 1988] failed to recognize one of the first rules
of analytical chemistry that any sample taken for characterization of an area
or population must necessarily be representative of the whole. The part must be
representative of the whole. Our analyses of the three thread samples taken
from the Raes and C-14 sampling corner showed that this was not the case.
- Robert Villarreal, Los Alamos National Laboratory (LANL) chemist who headed a team of nine scientists at LANL who examined material from the carbon 14 sampling region. (August 2008)
It may well go down as the biggest radiocarbon dating mistake in history; not because there is anything wrong with the measurement process (there may not have been); not because there is anything inherently wrong with carbon 14 dating (there is not); not because of shoddy sample taking (which indeed was shoddy); not because of red flags that should have raised serious questions (there were quite a few); and not even because basic tenets of archaeological dating were ignored by good scientists as was the case.
No, the reason is because, now, two decades later, whenever carbon 14 dating is discussed in high school or college classrooms, students like the student from Alaska are likely to raise a hand and ask some probing questions: What about the Shroud of Turin? Was it dated correctly? If not, how could so many scientists from so many reputable radiocarbon dating laboratories screw up so badly?
Inappropriate Question
It might be tempting to say that the subject is about a religious relic and thus discussion is inappropriate for the science classroom of a secular institution. But that is the wrong answer. This is a religious relic, but it is also an archeological artifact, one that has been rigorously studied scientifically. This happened in 1978 when several scientists examined it in Turin. This happened when the radiocarbon tests were conducted in 1988. This happened, also, when in 2004, a U.S. government publication revisited the tests. And in 2005, another secular, peer-reviewed scientific journal, Thermochimica Acta, published a paper that severely challenged the results of the 1988 radiocarbon dating. It didn’t stop there. Los Alamos National Laboratory chemist, Robert Villarreal recently reported that a nine member team of scientists chemically characterized threads from the carbon dating region of the cloth with some of the most advanced equipment available in that lab. And in August of 2008, the science journal, Chemistry Today, published a twelve page article on the shroud’s carbon dating. It is the wrong answer simply because the matter of the radiocarbon dating has nothing to do with religion.
It is the wrong answer because it denies the student a chance to take a critical look at the methods, procedures and data; from there to learn from the experience. Here is a chance to understand what can go wrong in radiocarbon dating and other scientific endeavors. Here is a chance to see how scientific conclusions are continuously being challenged by new information. And here is a stimulating case study for students to learn about radiocarbon dating and indeed more about our world and universe.
Carbon Dating: The Idea
After the war, Libby moved to the University of Chicago, where in 1949, he surmised that material from once living organisms could be dated by the amount of carbon 14 in the material. He realized that with a sensitive Geiger counter and a sufficient amount of carbon derived from something that had once been alive, he could arrive at a fairly accurate age for anything that had once been alive. In 1960, Libby was awarded the Nobel Prize in Chemistry for leading a team that developed Carbon 14 dating.
Ultraviolet and X-ray
Ultraviolet and x-ray photographs taken in 1978, before the carbon 14 dating samples were removed, indicated that there were chemical differences between the sample area and surrounding areas of the cloth. Moreover, Alan Adler, Emeritus Professor of Chemistry at Western Connecticut State University, had found a significant quantity of aluminum in yarn segments from the general area of the sample. It is not found on other samples from elsewhere on the shroud. Alum, an aluminum compound, the common mordant used with Madder root dye, was certainly an explanation. Many wondered if the labs or church authorities had considered this evidence or were even aware of it when they changed (or adopted) the protocol. The article in Inside the Vatican addressed this:
Asked whether he [Rogers] thought the authorities at Turin had been aware of such evidence as the 1978 photographs indicating that the corner of the Shroud from which they took the sample was unlike the rest of the cloth, Rogers responded that “it doesn't matter if they ignored it or were unaware of it. Part of science is to assemble all the pertinent data. They didn't even try.”
Robert Villarreal from the Los Alamos National Laboratory
In a presentation The Ohio State University’s Blackwell Center, Los Alamos National Laboratory (LANL) chemist, Robert Villarreal, disclosed new findings showing that the sample of material used in 1988 to Carbon dating could not have been from the original linen cloth because it was cotton. According to Villarreal, who lead the LANL team working on the project, thread samples they examined from directly adjacent to the sampling area were “definitely not linen” and, instead, matched cotton. Villarreal pointed out:
the [1988] age-dating process failed to recognize one of the first rules of analytical chemistry, that any sample taken for characterization of an area or population must necessarily be representative of the whole. The part must be representative of the whole. Our analyses of the three thread samples taken from the Raes and C-14 sampling corner showed that this was not the case.
Villarreal also revealed that, during testing, one of the threads came apart in the middle forming two separate pieces. A surface resin, that may have been holding the two pieces together, fell off and was analyzed. Surprisingly, the two ends of the thread had different chemical compositions, lending credence to Rogers’ finding in Thermochimica Acta.
After conducting analysis at high vacuum with the ToF-SIMS, the “spliced thread” broke into three distinct pieces; a fuzzy end (Region 1), a tight woven end (Region 2), and a micro-sized circular cocoon-shaped brown crust that seemed to be connecting the two end pieces. The ToF-SIMS results were the first to show that the spectra from the two ends were similar to cotton rather than linen (flax) and the Spectroscopist recommended that the next analysis should be with the FTIR instrument. After several scans of individual fibers or strands, the FTIR data showed that the two ends (Region 1 and 2) were definitely cotton and not linen (flax). The crust appeared to be an organic-based resin, perhaps a terpene species, with cotton as a main sub-component. After showing the FTIR data to Barrie Schwortz and Sue Benford, they were quite surprised at the results and decided to send me two other pieces of thread (No. 7 and 14) that were from the same sampling area and that had been in John Brown’s Lab in Marrietta, Georgia.
The results of the FTIR analysis on all three threads taken from the Raes sampling area (adjacent to the C-14 sampling corner) led to identification of the fibers as cotton and definitely not linen (flax). Note, that all age dating analyses were conducted on samples taken from this same area. Apparently, the age-dating process failed to recognize one of the first rules of analytical chemistry that any sample taken for characterization of an area or population must necessarily be representative of the whole. The part must be representative of the whole. Our analyses of the three thread samples taken from the Raes and C-14 sampling corner showed that this was not the case. What was true for the part was most certainly not true for the whole. This finding is supported by the spectroscopic data provided in this presentation.
The recommendations that stem from the above analytical study is that a new age dating should be conducted but assuring that the sample analyzed represents the original main shroud image area, i.e. the fibers must be linen (flax) and not cotton or some other material. It is only then that the age dating will be scientifically correct.
Chemistry Today Article
An article in Chemistry Today (August 2008) summarizes nicely:
Since the dating, many hypotheses have been proffered attempting to explain the C-14 results, which appear contradictory to a plethora of data pointing to a more ancient origin. An acceptable hypothesis of why the Shroud dated between AD 1260-1390 must satisfactorily explain the precise, statistically-determined angular skewing of the dates corresponding with the individual laboratories, with reference to the location of the sub samples received. The hypotheses of generalized ionizing radiation, thermal effects, environmental carbon monoxide enrichment and bio plastic coating are incapable of meeting this latter requirement, as is the premise that the cloth itself, is, in toto, medieval.
John Jackson on Complexity of Image
Physicist John Jackson has observed that "mathematical analysis of image resolution suggested that no single, simple molecular-diffusion or radiation mechanism could produce the image observed." Roger agrees. And Rogers proposes:
[A] combination of systems could offer an explanation,
e.g., anisotropic heat flow by radiation from the body to the cloth, attenuated
heat-flow in the cloth, gaseous diffusion, convection, surface properties of
cloth, and the dependence of chemical rates on temperature.
Were it not for some significant characteristic of the images, this potential explanation (something of a chemistry equivalent of two wrongs make a right) might suffice. Rogers alludes to the problem:
A dead body at normal temperatures and humidity will produce reactive amines—absolutely. A primitive (Roman times) piece of linen that is contaminated with crude starch will react with the amines—absolutely. Some color will be produced. If the Shroud is truly old and it covered a dead body, the amine/saccharide colors ARE present. Can they have been produced in a distribution that reflects the characteristics of the body? Theoretically the answer is yes; however, a number of demonstrations are required to illustrate the problem to everyone's satisfaction. . .
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