cotton

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.

Cotton

Several years earlier, a textile expert, Gilbert Raes (for whom the Raes corner is named), had been permitted to cut away a small fragment of the shroud. In it he found cotton fibers.  Rogers confirmed the existence of embedded cotton fibers and noted that such cotton fibers are not found in other samples from anywhere else on the shroud. Cotton fibers were sometimes incorporated into linen threads during later medieval times, but not earlier, and not even as early as the carbon 14 range of dates. This, along with the dyestuff, suggested some sort of alteration or disguised mending.

Rogers also noted that fibers in the Raes material contained less lignin than the rest of the shroud. Lignin is a chemical compound found in plant material including flax, the plant from which linen fibers are sourced. The most plausible explanation for this difference was that material in this area contained threads that had been bleached more efficiently. It was already known from the shroud’s faint variegated appearance that the shroud’s thread was probably bleached before weaving, probably with potash. This is not an exacting method and thus some hanks of yarn were whiter than others. As the cloth aged and naturally yellowed, the variegation became more pronounced, as can be seen in contrast-enhanced photographs. This form of ancient bleaching removed very little lignin.

Arguably, from a historical point of view (but not a scientific one) the linen cloth used for the shroud was not produced in medieval Europe. Even by the timeframe suggested by the radiocarbon dating, linen was “field bleached” after weaving. And it removed most of the lignin.

Red Flags Ignored

There were other clues, as well. All of them were warning signs that something might be wrong with the carbon 14 samples:

• Giovanni Riggi, the person who actually cut the carbon 14 sample from the Shroud stated, "I was authorized to cut approximately 8 square centimetres of cloth from the Shroud…This was then reduced to about 7 cm because fibres of other origins had become mixed up with the original fabric …" (emphasis mine)
• Giorgio Tessiore, who documented the sampling, wrote:  “…1 cm of the new sample had to be discarded because of the presence of different color threads.” (emphasis mine)
• Edward (Teddy) Hall, head of the Oxford radiocarbon dating laboratory, had noticed fibers that looked out of place. A laboratory in Derbyshire concluded that the rogue fibers were cotton of “a fine, dark yellow strand.”  Derbyshire's Peter South wrote: “It may have been used for repairs at some time in the past…”
• Gilbert Raes, when later he examined some of the carbon 14 samples, noticed that cotton fibers were contained inside the threads, which could help to explain differences in fiber diameter. This may also explain why the carbon 14 samples apparently weighed much more than was as expected.
• Alan Adler at Western Connecticut State University found large amounts of aluminum in yarn segments from the radiocarbon sample, up to 2%, by energy-dispersive x-ray analysis. Why aluminum? That was an important question because it is not found elsewhere on the Shroud.
• The radiocarbon lab at the University of Arizona conducted eight tests. But there was a wide variance in the computed dates and so the team in Arizona combined results to produce four results thus eliminating the more outlying dates (reportedly they did so at the request of the British Museum, which was overseeing the tests). Even then, according to Remi Van Haelst, a retired industrial chemist in Belgium, the results failed to meet minimum statistical standards (chi-squared tests).  Why the wide variance in the dates? Was it because of testing errors? Or was it because the sample was not sufficiently homogeneous? The latter seems very likely now, and the statistical anomaly indicates something very suspicious about the samples.
• Bryan Walsh, a statistician, examined Van Haelst’s analysis and further studied the measurements. He concluded that the divided samples used in multiple tests contained different levels of the C14 isotope. The overall cut sample was non-homogeneous and thus of questionable validity. Walsh found a significant relationship between the measured age of various sub-samples and their distance from the edge of the cloth. Though Walsh did not suggest invisible reweaving, it is consistent with his findings.

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.

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