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Concerns on this Paper

Posted by MarcoBella on 21 Aug 2017 at 18:19 GMT

There is a number of issues regarding this work.
a) The analysis proposed by the Authors for the identification of creatinine is questionable. The standard methods to identify organic compounds are based on NMR spectroscopy or mass spectrometry. The Authors obtain a diffractogram of a specific region of the sample, simulate the diffraction pattern of creatinine and on the basis of their comparison they assume that creatinine is indeed present (see figure 6). What is the need to use a simulation instead of a real sample of creatinine? Creatinine is a cheap and readily available compound, which costs few euros per gram. What is the effect of ageing on the diffraction pattern of creatinine? As far as I can read, no other substance has been tested or simulated. Why do the authors believe that the substance they are analyzing is actually creatinine and not, for example, polyethylene, sebum, any amino acid or a mixture of these compounds?
b) The origin of the sample. The linen fiber used by the Authors (about two millimeters long) was originally collected by Ray Rogers in 1978 by an adhesive tape from the surface of the Shroud. Some of these tapes were given to microscopist Walter McCrone, who, in Rogers’ words, “contaminated” them. [1] Then, they had to be “laboriously cleaned” by Rogers’ wife, with a procedure that involves washing with an organic solvent. After several years, the samples were given to the Authors. What was the influence of all these treatments on the sample? This aspect is not discussed in the paper, even if the questionable origin of Rogers’ samples was described in the literature. [2-3]
To validate the conclusions by the Authors, one must assume that:
1) their analysis is actually suitable to identify creatinine with a good degree of confidence;
2) ageing for thousands of hundreds of years has no effect on the presumed creatinine particles;
3) the collection by a sticky tape gives a representative sample;
4) the adhesive on the sticky tapes has no influence on the presumed creatinine particles;
5) the fiber they have is representative of the other fibers on the tape;
6) the eventual “contamination” by Walter McCrone is non-influent;
7) the eventual “laborious cleaning” by Rogers’s wife is non-influent;
8) their “simulation” (figure 6) is still reliable despite not taking into accounts events 2-7.
The fact that the sample might have been “contaminated” and then “laboriously cleaned” is something that at the very least should have been indicated to the referees and the readership.
c) In addition to the above concerns, also the cited bibliography is questionable. As an example, the Authors give credit to Rogers’ work (see ref 9) which suggests that “…indicated an age for the TS “between 1300-and 3000-years old…” without citing the following works on the same journal that raised strong concerns about the treatment of Rogers’ samples. It is noticeable that the “invisible mending theory”, supported by Rogers in that article, some years later has been defined “pseudoscientific” twice on the same journal that had published it.
d) More substantially, one of the key statement of the Authors,
“The bond between the iron cores of ferritin and creatinine on large scale occurs in a body after a strong polytrauma)” does not appear to be supported by the cited literature (refs. 41-43).
For example, in ref 41 no ferritin or iron is cited. The paper rather discusses the concentration of creatinine after a trauma. To measure “concentration” one should know the amount of a solute and the volume of the solution. The simple presence of the presumed creatinine is not enough to say if the concentration was high or low.
The evidence presented by the Authors does not support in any way their conclusion, (“the man wrapped in the TS suffered a strong polytrauma”), which is instead based on the simple over-interpretation of data coming from a sample with an unknown story and a chain of questionable assumptions. The Authors do not discuss the issue of how their fiber could be considered a representative sample, and omit to say all the treatment they underwent. It is very surprising none of the concerns expressed above have been raised during the peer-review process.

[1]“He nearly destroyed the value of the carefully prepared samples” (R. Rogers, A Chemist's Perspective On The Shroud of Turin, Schwortz, 2008, p. 23).
[2] Rogers wrote: “…Walter McCrone had ignored agreements on how the STURP samples were to be observed, and he contaminated all of our samples by sticking them to microscope slides. All of the fibers were immersed in the tape's adhesive, Joan Janney (now Joan Rogers) laboriously cleaned and prepared Shroud fibers for analysis at the MCMS...[Midwest Center for Mass Spectrometry]” https://www.shroud.com/pd... R. N. Rogers A Chemist's Perspective On The Shroud of Turin (J. Rogers, B. M. Schwortz eds) (2008) Lulu, Florissant.
[3] Bella M., Garlaschelli L, Samperi R. “Comments on the analysis interpretation by Rogers and Latendresse regarding samples coming from the Shroud of Turin”. Thermochimica Acta, 2016, 632, 52-55. (http://www.sciencedirect....)

Marco Bella, Department of Chemistry, Sapienza University of Rome, Italy
Luigi Garlaschelli, CICAP, Comitato Italiano per il Controllo delle Affermazioni sulle Pseudoscienze

No competing interests declared.

RE: Concerns on this Paper

ecarlino replied to MarcoBella on 04 Sep 2017 at 11:10 GMT

In the following the answers on each points:
Answer to a) As discussed in the paper, we used a new approach to study the fiber and it is indeed the use of this method that enables to detect properties not observed before and to discriminate the eventual presence of artifacts. The method has been developed about five years ago and applied successfully in other experiments on nanostructured cocrystals, as reported in the paper with the relevant bibliography. It is quite common in science that advances of the knowledge are related to new approaches in the investigations. We indeed studied plenty of nanoparticles on the fiber of the shroud (other examples are available in the published supplementary information) and we apply well-established methods of Transmission Electron Microscopy to identify univocally the structure of the nanoparticles. There is a wide literature on this subject, see for example the book of Reimar mentioned in the paper. The effect of aging on the specimen has been discussed in the paper and it is at the origin of the lack of spatial resolution in the EDXS spectra due to the pile up of carbon contamination when the electron beam is focused on the specimen. A further direct evidence of the aging, see the paper, it is evident in the distortion in the lattice fringes visible in the HRTEM images published (for more examples see also the supplementary information), which indicate the presence of the crystal defects in the structure. In the paper it is reported that we also tried a comparison with the structure of urea and ferritin and we did not find any agreement in these cases. The comparisons with urea and creatinine structures have been made on the basis of the evidence that the spacing at 0.25nm is absent in our experiments. As reported in the paper, the absence of 0.25 nm in ferrihydrite is due to its bonding to urea or creatinine, as demonstrated in the reference reported in the paper. This is why we checked for creatinine and urea, as discussed in the paper. The experimental evidences univocally point the nature of the nanoparticles as described in the paper.

Answer to b) The fiber analyzed contains creatinine bound to ferrihydrite. TEM methods have been used plenty of time in the last fifty years to identify the structure of the matter at high spatial resolution and there are thousands of papers on this subject. The fiber was analyzed by TEM as received, without any pretreatment. The eventual actions on the fiber during the centuries and after the extraction from the shroud did not cancelled this evidence and it is highly unlikely that the fiber, and only that fiber in the shroud, was contaminated with the blood serum of someone who suffered a strong polytrauma before to die. The sticky tape or the cleaning process very likely contributed to the hydrocarbon-like contamination evidenced in our experiments and reported and shown in the figure 2.

Answer to c) In the references for the introduction we indicated a number of papers to give to the reader evidence of the wide scientific debate on the shroud, on the antithetic point of views and of the need of experiments capable to answer to the many open questions on this subject overcoming possible artifacts made along the centuries.

Answer to d) In the paper 41 it is given correctly evidence of the relationship between the occurrence of a strong polytrauma and the acute kidney insufficiency, which is very often fatal and produces a growth of wastes in the blood and, as known, creatinine is one of them. It is meaningless to measure any concentration on a single fiber because certainly the shroud was not wet homogenously. What it is important in the framework of the experiments performed by TEM on the fiber, it is that in all the cases in which was possible to measure on the same electron diffractogram angles and spacing together, they belong to creatinine and, furthermore, the creatinine particles are bound to ferrihydrite nanoparticles. The bound of creatinine to ferrihydrite occurs in the blood serum after a strong polytrauma as the ferrihydrite is contained within the blood cells that are broken as a consequence of the polytrauma releasing their content in the blood stream.

No competing interests declared.