Apologies to early birds: I shall be composing this posting in real time. Yes I know I should be assembling in draft mode, and only hit the Send button when complete and polished. But I’m more a comments than posting man – writing something as if a comment somehow makes for a more focused less rambling endproduct – maybe it’s the online buzz factor, I’m not sure. But it should not take more than an hour or two, and it’s always good to see one’s spiel taking shape in bite-size instalments that one can edit rather than set-in-tablets-of-stone pub lish-and-be-damned form. Now the, will that YouTube video of Barrie’s correctly embed I wonder (I have not tried doing that in WordPress before, but it should, given it’s on Dan Porter’s site (which I am now content to follow purely as a spectator – see previously- the cost/benefit seesaw having tipped back to the left).
OK, let’s insert that embed code and see if allows visitors to run the programme. If it doesn’t itwill have to be a screen grab with a dead GO button.
Next: insert a transcript (approx) of what Mr.Schwortz said to the interviewer. (That will mean transcribing som eof my hasty scribbles, having been unable to locate a transcipt of the programme).
Then insert Thibault Heimburger’s summary of what he has been able to access from the Adler archive. (That will take a little time, given the user-unfriendly nature of pdf archives where C&P is concerned). But already I know there’s little to transcribe here – a remarkable paucity one might say of hard data – given the enormous publicity of the ‘bilirubin story’, promoted to this day by STERA’s President as if proven fact. (Where’s the beef? Or rather, where’s the bilirubin, except in someone’s over-vivid imagination?)
OK, here are my scribbles from watching the first half of the programme:
First, there’s a lot of references to 3D-encoded information, allegedly “unique” and to “scorches” having been ruled out. We’ll return to that another day. Barrie then says it’s “frustrating how things were spun in the press” (with which I profoundly agree) followed shortly by this, regarding the largely self-selected STURP (over-represented by engineers, and under-represented by scientists in my opinion): “I don’t think that any group of scientists could have done any better”. Er, how can you, drafted in as a photographer, be so certain about that, Mr. Schwortz? Later, you describe Dr. Alan Adler as a “world-renowned blood expert”. No, he wasn’t. He was a highly regarded synthetic organic chemist, but probably little known outside his speciality (the fate of most middle-ranking scientists, myself included) who was specializing in porphyrins and other cyclic tetrapyrroles . That did not make him a blood expert, and there’s nothing under his listed publications in Google Scholar to support his description as a blood anything. Yes, a particular porphyrin (protoporphyrin IX) is at the oxygen-binding iron centre of haemoglobin, but if you check you will find that Alan Adler is best known for the total synthesis of a model porphyrin with non-physiological phenyl side chains that is totally unlike protoporphyrin IX.
modified synthesis which represents:~ n improvement over previous literature methods-”
for meso-tctraphenylporphin (TPP), The yield and rate of the condensation of pyrrole and …
Continuing (my patchy transcript): .
“… looked at the Shroud and saw that that the blood was still reddish or crimson in colour … both knew that old blood is supposed to turn brown or black, not red, and not stay red, and that was a kinf of deal breaker. … The blood chemist on our team , world-renowned blood chemist Dr.Alan Adler, did the analysis and proved that the blood was not paint or pigment…it had haemoglobin and porphyrin and other components of blood. We proved it was actual… Dr. Adler found a very high content of bilirubin and that is commonly the case when someone is tortured over a period of time, the body goes into shock the liver starts producing bilirubin and pumping it into the bloodstream. Adler had found a very high content of bilirubin… Bilirubin is a haemolytic agent: it breaks down red blood cell walls, and when that happens the blood stays red forever. But I did not find that out until 18 years later…”
Phew! Where does one start. More to the point, how does one start, without coming over as a smartass? But hold on a sec’. I am a smartass where the topic of bilirubin is concerned. It was my first paid research project (University of Pennsylvania Hospital Medical School, 1970-72. if I went in front of TV cameras and told the world how to take the most professional photographs in the world, based on my knowledge of silver salts learned at school, I would expect the Barrie Schwortz’s to get irritated and indignant. yet that is precisely what he has done, in reverse, namely to present a bowdlerised (or addled, nay Adlerized) version of chemistry and physiology that is frankly … to good to be true (good, that is, if one is seeking instant “science” to back up one’s preconceptions about the Shroud.
Where indeed does one start? Let’s begin with the pdf that respected Shroud scholar Thibault Heimburger MD has produced, detailing and summarising STURP’s investigation of the bloodstains. (While I did not care for Thibault’s hot-template image-imprinting technology that concluded a scorch did not produce the Shroud image, I nevertheless respect him for the due diligence he has exercised elsewhere in Shroud studies).
From TH: (apols for formatting errors – it’s taken 20 minutes just to remove all the crazy line breaks that occur when cut-and-pasting from a pdf)
Later, Adler wrote that the spectra of the non-birefringent red-coated blood fibrils from the Shroud did not match the spectrum of methemoglobin in blood solution as it is given in the literature. However, he found “ a spectrum that was characteristic of only one known group of compounds – the so-called high-spin, high- iron porphyrins ”which are found in a special form of methemoglobin: methemoglobin in its para-hemic form. Now, this kind of para- hemic species formed spontaneously in living persons when high quantities of hemoglobin are released in the serum from broken red cells, i.e. under hemolysis conditions. Finally, they tested for bile pigments with the Ehrlich’s reagent with the same microspotting method.
The characteristic azobilirubin color could be detected on the olive colored shards found mainly around the blood areas, on the orange globs and weakly on the more orange colored fibers. Further, the test color was sensitive to acid, turning a paler purple and was discharged by 10 minutes of short wave UV light as is characteristic of this color test. These 2 tests clearly show that unusual high amounts of bilirubin or bile pigments are present in the blood and serum areas. This fact should also explain the unusual red color of the blood on the Shroud by the mixture of brown met -hemoglobin with yellow orange bilirubin. Normal blood contains only small amounts of bilirubin. Hemolysis (the breakdown of the red cells) in living bodies can result from prolonged hard traumatic shocks and pr oduce large amounts of bilirubin as found in the blood of the Shroud.
Adler, as a recognized expert in blood and porphyrins, presents here an impressive set of proofs that hemoglobin (methemoglobin) is present on the Shroud.
There is porphyrin, the characteristic part of hemoglobin, and this porphyrin is not from chlorophyll because, according to Adler, “ its fluorescence does not have to be generated ” i.e. the fluorescence appears spontaneously under UV, which is not the case here, as demonstrated by the UV fluorescence studies on the whole Shroud. There is hemoglobin as demonstrated by the microchemical spot tests (hemochromagen and cyanmethemoglobin tests) and the characteristic Soret band. While the absorption spectra of haem derivatives differ from derivative to derivative, all have in common this strong absorption at about 400 – 425 nm. This hemoglobin (methemoglobin) is in a very special form (para – hemic) which develops spontaneously at the surface of hemoglobin films and in living bodies that undergo hemolysis, as in severe traumatic conditions. Hemolysis in the l iving also produces bilirubin which was found in the blood at extraordinary high levels, particularly in the olive colored shards found in the serum areas around the blood stains as expected. In addition, this discovery explains the unusual red color of this old blood as the result of a mixture of brown orange methemoglobin in the para – hemic form and yellow – orange bilirubin. As Adler wrote: “ No one would have ever dreamed, when we first started doing the analysis, that the chemistry would provide corroborating evidence to what the pathologists concluded long ago about the Shroud figure .”
How many folk, hearing Barrie Schwortz make those confident, categorical statement about bilirubin and permanently red blood, would have guessed that the evidence for those statements rested on microchemical tests performed, for the most part, on fibres retrieve dfrom the Shroud with sticky tape, that Adler and his co-worker John Heller had not been part of the team that went to Turin to collect samples, that the tests performed e.g. the Ehrlich test for bilirubin is non-specific, and that other, non-bilirubin substances can produce a false positive.
Reminder to myself: insert technical note on the Ehrlich reagent – being careful to get the right one for “bil,irubin” – there being variants.
Forexample: if you look at the wiki entry on Ehrlich’s reagent, you are told it is DMAB ( dimethylaminobenzaldehyde . But it’s Ehrlich’s diazo reagent that is used in bilirubin detection, which is diazotised sulphanilic acid (generated in situ from sulphanilic acid, sodium nitrite and acid), and the diazonium ion – active ingredient so to speak – can couple up not only with bilirbin to make a red or purple dye but to a host of other things included notably phenols. For example, any thymol preservative contaminating the Shroud would give a positive test, thymol being a phenol.
In fact, when using Ehrlich’s diazo reagent to test for bilirubin, properly mindful of the presence of interfering subtances if one is a jaundice specialist (which Adler was not) , it is better to speak of the Van Der Bergh reaction.
With any test based on dye formation one must always be wary of interfering substances (phenols etc) that might be present in “blood” of unknown origin or history. One cannot make the same assumption with ancient material as one would with blood drawn freshly from a patient. So even at the broad brush qualitative level it is doubtful whether it was bilirubin that produces the colour change. In fact, there are strong theoretical grounds, briefly acknowledged by Adler himself later, in an entirely different context (Shroud preservation) that bilirubin could NOT have been present, given that is unstable to light and oxygen, and in fact self-sensitizes its own oxidation and decomposition to smaller dipyrroles etc via a singlet oxygen mechanism (the subject of my own first published paper).
Cut-and-paste from Google Scholar:
chromatographically and spectrally identical with certain products generated by photo-
oxidation of bilirubin in CHCl 3. The pure pigments exhibit the spectrochemical …
Returning to Adler, and Thibault’s admirable and concise summary thereof – it gets worse, much worse. Not content with stating that some bilirubin seemed to be present, based on non-specific microchemical spot tests, we are then told that the amounts present were “extraordinary”, and not just once but twice. But there’s one tiny omission = we’re not given any estimates or numbers that allow us to decide how extraordinary. Elsewhere I once read Adler saying the amount of bilirubin was as great or greater than that of oxidized (met)-haemoglobin , but a relative measure like that is of no use whatever if one does not know how much of that was present – and yes, you may have guessed, we weren’t told that either.
Having as I said worked with bilirubin I find it improbable that any quantitative estimates were possible, given the kind of technology applied. To be certain bilirubin was present, and to measure it, one would need to isolate and measure it. Was that asking too much in 1978, bearing in mind Barrie Schwortz’s claim to the best of technology having been applied? Certainly not if one had been dealing with isolated blood scrapings. The technology available then, which I and Don Ostrow and John Zarembo were using in Philadelphia, involving solvent extraction, thin layer chromatography and mass spectrometry could have provided reasonable ballpark estimates at least. But if restricted to working mainly with coloured fibres it was never realistically possible to identify bilirubin as a significant constituent of ancient blood, which should NOT have been there on strong theoretical grounds, and to propose it acts to produce a permanent red colour in blood is to stretch chemical credulity beyond breaking point. Yet Barrie Schwortz continues to proselytize that bilirubin/red blood story as the clincher for Shroud authenticity (so much so that whenever a new thread opens on media forum on the TS and its authenticity, someone invariably pops up with bilirubin as the supposed trump card).
Let’s not mince our words. Bilirubin was a figment of Alan Adler’s imagination. It was not there, and just as soon as the Vatican allows access again to the Shroud, and allows some more small blood scrapings to be taken, say from the less iconic dorsal side, then I confidently predict that NO BILIRUBIN WILL BE DETECTABLE.
But in the short term I believe it is time that someone sporting the title President of the Shroud of Turin Education and Research Assn should stop telling that bilirubin story unless or until he can produce hard evidence to back it up. Spot test colour changes, or peaks /troughs in absorbance do not constitute hard evidence. When quoted as evidence by someone who goes on to provide a physiological scenario for high bilirubin involving the trauma of crucifixion, one is entitled to question the scientific objectivity of the individual in question. Hypotheses are supposed to square with the facts. One does not dream up facts to support pie-in-the-sky hypotheses.
Do I sound angry? You betcha I do. Very angry. What I have described here is shoddy science, and if Alan D Adler were still alive today, I would be telling him that to his face, referring to Mickey Mouse science (which the host of shroudstory.com objected strongly to when I applied the same to a living so-called scientist. Think what you want, Daniel Porter, but I try to be consistent, making no distinction between living and dead scientists when it comes to evaluating their claims. Rubbish claims have to be banished from the literature. People who espouse or promote rubbish claims in the name of science have also to be singled out and brought to heel (or given an opportunity to defend themselves) It’s essential for the progress of science – to say nothing of its reputation.
More to come (work in progress)
As for the detailed embroidering of the bilirubin story, one might ask why we have (apart I believe from one WW2 reference) only the biblical crucifixion as a precedent for “extraordinary” levels of bilirubin. If acute trauma routinely produced steep rises in bilirubin and jaundice, it would be part of the language (” 2 days later he was pulled out from under rubble of his collapsed house, yellow with trauma”).
Bilirubin a haemolytic agent? That’s the physiological equivalent of a man bites dog story. Yes, there are isolated references to it having that effect (any amphipath in excess tend to penetrate and weaken red cell membranes) but it’s the other way round in textbook physiology and biochemistry. Something happens, e.g oxidative stress, toxins etc to make red cells rupture and release their haemoglobin. The latter are then degraded to bilirubin in the liver, kidneys etc, and when there’s a conjugation deficit cause colouring of skin to produce visible jaundice. Only very rarely would there be a positive feedback, in which surplus bilirubin weakens further red cells, given the avidity of its binding by serum albumin and intracellular carrier proteins.One would probably need to have a separate agent, a competing organic anion, occupying the bilrubin binding sites to set up a vicious cycle. One cannto routinely describe bilirubin as a haemolytic agent, Mr.Schwortz, narrative-friendly though that may seem. Science is generally not narrative-friendly. Properly conducted, it creates its own narratives.
So where did Alan Adler go wrong? He and the rest of STURP were tasked with establishing the facts on the Shroud that would help reach a decision re authenticity. That was done competently as regards the issue as to whether it was a painting or something else. The conflicting findings of Walter McCrone v The Rest should have signalled that the Shroud needed to be approached with a completely open, and dare one say unbiased mind. But we saw STURP members one after another who, on discovering peculiar or anomalous findings, straight away took refuge in biblically correct”explanations” often top heavy with qualifying assumptions, based on the assumption that the Shroud was 1st century, and their interpretative skills were then needed to find a precise fit with the safety net narrative narrative ( even to the extent of fleshing out the parts that the apostles never got round to telling us). In Adler’s case, the discovery of an anomalous porphyrin spectrum should have prompted a chromatographic isolation of the rogue species separate from all other substances, a re-examination of its spectrum and, if need be, a run through a mass spectrometer to see how its fragmentation pattern compared with known standards or models. Why did he not do that? Why did he immediately latch onto that bilirubin idea, and having convinced himself on the basis of spot tests etc that “extraordinary” amounts of bilirubin were present, why did he not attempt to isolate that by solvent extraction and chromatography, and provide documented evidence at least for its physical presence, instead of lumbering the literature with a Wimbledon pre -Hawkeye exclamation (“I saw chalk dust”), correction , “I saw an exceptionally red spot of colour under my microscope, betraying the presence of “extraordinary” amounts of bilirubin.”
Yes, Mr. Schwortz, the quality of science behind Adler’s claim for bilirubin, the one you are so keen to proselytize, is roughly on a par with John McEnroe’s “I saw chalk dust”.
For any entirely different take on those bloodstains that stubbornly remain red, century after century, see this posting from August 2012.
PS: The observant reader who has stayed with me thus far may have noted that I have said next to nothing about Alan D Adler’s approach to Shroud blood from the perspective of porphyrin chemistry, his acknowledged area of expertise. That’s easily explained: there’s more than enough on one’s plate addressing his extraordinary stance regarding those ‘extraordinary’ amounts of bilirubin, without getting too involved with the other side of the coin, namely his proposed “high spin” high iron methaemoglobin species which he claimed was also trauma-related (yet another instance of deserting the organic chemist’s terminology and launching off into the realms of crucifixional neo-physiology and neopathology (or should that be crucifictional?). As I said at the beginning, one hardly knows where to start in addressing the sheer confidence, ebullience , dare one say audacity of Dr. Adler’s breakout from the confines of synthetic organic chemistry, of reflux stills, condensers, spectrophotometers etc. progressively extending his reach into biomedical disciplines. (The extent to which he was aided and abetted in this widening of repertoire by the more physiologically/medically inclined John Heller is something I have yet to establish). At some point I need to provide a brief overview of the porphyrin half of the equation, or rather oxidized haem (protein + iron(III) + porphyrin). It’s the subtleties that attach to the spectral changes accompanying changes in the iron on storing and ageing that make me hesitate. But again, if one stands back and takes in the broad perspective, one has again to ask:why did a porphyrin chemist , faced with an atypical spectrum, choose to invoke not just one but two allegedly trauma-related chemical entities – bilirubin and his exotic high spin methaemoglobin- both fitting the biblical narrative and thus ASSUMING authenticity. Why did he not maintain strict scientific objectivity, and confine himself to isolating by chromatography both the putative iron-free protoporphyrin IX and bilirubin which combined with iron and protein were in his view responsible for the atypical spectrum and that BOGOF eternally-red blood? He may have found the porphyrin was or was not authentic protoporphyrin IX, and that there was or was not bilirubin accompanying it (I’ll refrain from stating what I think he would have found). Had he done so we would now have more hard facts on which to base different ideas – pro or anti-authenticity. Instead, Adler chose to jump the gun, and impose on the world of Shroudology his (some might say) quirky, nay wacky ideas that were poorly if at all based on fact – more fancy than fact one could say – and here we are more than 30 years later watching videos in which the President of STERA builds up a synthetic organic chemist as a world-renowned blood chemist, and uncritically promotes his untested, unproven ideas as if they were established fact, obtained under the STURP imprimateur.
This is not the kind of science which put a man on the moon… To find this kind of science, one has to go back earlier in US history, to the opening up of the West, to snake oil salesmen…