The Voynich Ninja

(01-01-2025, 03:49 PM)Koen G Wrote: You are not allowed to view links. Register or Login to view.

(31-12-2024, 07:06 PM)Mark Knowles Wrote: You are not allowed to view links. Register or Login to view.I also mentioned those as part of a more general point. It would be nice if everytime someone comes across a manuscript or document that is not digitised and which they think is interesting they could add it to a list with a brief reason why they think it is interesting.

The problem is that it's very hard to know for sure whether a MS is interesting. Take my Willehalm research for example. This MS was not digitized when I wrote my blogpost, but now it is: You are not allowed to view links. Register or Login to view. 
Before, I had only one image from it, and at a glance I already noticed that the style was very different from the VM. Still, seeing the images of the embracing couple in there would have been interesting, but it doesn't add anything to our understanding. It's not even worth mailing the library about.

For me to know of a MS that might actually be worth the effort, I would need to know that it is the "missing link" I'm after. And that is very tricky. In practice, it turns out than none of the MSS I could have looked for are of much help. It's kind of like looking for a needle in a haystack, but you don't know if the needle is there. Getting to see more pieces of hay probably doesn't help much.

Of course, there can be instances where you have a very good idea of a single potentially interesting document. But in that case, I try to reach out to the library directly.

I can tell of my experience of research into early 15th ciphers. There are some ciphers which can now be found online like the Tranchedino and the Urbinate. There are some ciphers that are contained in books or articles which can be now be downloaded like the Meister books. There are some ciphers in books which cannot be downloaded like Lydia Cerioni books. There are some ciphers which are referred to in listings in books or articles for which it is necessary to contact the archives to which the listing refers to request photoreproductions of those ciphers like the ciphers referred to in Meister. There are some ciphers for which references can be found through googling and for which it is necessary to contact the archives to request photoreproductions such the Pileo de Marini ciphers in the Genoa Diocesan archives or the Albertoni cipher ledger. There are some ciphers which I learnt of by being referred to them by other academic researchers such as the Milanese ciphers in the BNF. There are some ciphers that I learnt of from archivists from archives that I contacted. I have seen all the ciphers that I know of, except for the 14th century Genoese accounting cipher which I haven't bothered to track down. Now, I am left with references to ciphers that I have not seen and don't know if they survive and if they survive where precisely they survive such as the 1431 Milanese enciphered letters intercepted by the Papacy which may survive in the Vatican archives and the 1427 Milanese cipher referred to in Luigi Osio's book. This leaves me with the desire to search the Vatican archives for examples of early 15th century ciphers and try to trace which Milanese archive the 1427 cipher might be in if it has survived. I know that if I had only limited myself to ciphers that I could find online then this would have drastically reduced the amount of ciphers that I could find. As it is, it is still a very difficult task as so much of the cipher records that existed have been destroyed in fires or other ways, so overall very little survives.

I moved a number of posts here at nablator's suggestion: You are not allowed to view links. Register or Login to view.

I'll also move this thread to Voynich Talk.

(23-11-2024, 02:11 AM)asteckley Wrote: You are not allowed to view links. Register or Login to view.But Rene -- it is precisely BECAUSE the presence of anatase would have been such a major find and everyone involved knew it (presumably), that we would expect their report to be particularly specific on details regarding titanium compounds!  They would go out of their way to be explicit on whether it did or did not contain anatase, or if they were simply unable to identify that fact one way or the other.

The titanium was found in the writing ink, and we can all clearly see that the writing ink isn't white.

(29-11-2024, 03:55 PM)proto57 Wrote: You are not allowed to view links. Register or Login to view.But O'Neil actually told us that, "The most startling identification… …was folio 93, which is quite plainly the common sunflower.

A sunflower has petals. The flower on folio 93 clearly doesn't. It looks more like a mushroom than a sunflower.

(07-03-2025, 11:07 PM)zachary.kaelan Wrote: You are not allowed to view links. Register or Login to view.

(23-11-2024, 02:11 AM)asteckley Wrote: You are not allowed to view links. Register or Login to view.But Rene -- it is precisely BECAUSE the presence of anatase would have been such a major find and everyone involved knew it (presumably), that we would expect their report to be particularly specific on details regarding titanium compounds!  They would go out of their way to be explicit on whether it did or did not contain anatase, or if they were simply unable to identify that fact one way or the other.

The titanium was found in the writing ink, and we can all clearly see that the writing ink isn't white.

(29-11-2024, 03:55 PM)proto57 Wrote: You are not allowed to view links. Register or Login to view.But O'Neil actually told us that, "The most startling identification… …was folio 93, which is quite plainly the common sunflower.

A sunflower has petals. The flower on folio 93 clearly doesn't. It looks more like a mushroom than a sunflower.

Sunflower without Petals:

You are not allowed to view links. Register or Login to view.[attachment=10131]

(07-03-2025, 11:43 PM)Dana Scott Wrote: You are not allowed to view links. Register or Login to view.Sunflower without Petals:

You are not allowed to view links. Register or Login to view.

I again see more resemblance to a mushroom. No spikes or outgrowths of any kind, and the lines at the edges and little bump at the top look more like a mushroom. Obviously a mushroom doesn't have leaves, but the general consensus is that there's a combination of features of multiple plants among the drawings.

(22-11-2024, 08:31 PM)proto57 Wrote: You are not allowed to view links. Register or Login to view.The issue with the Vinland Map titanium was, as you say, that it was in the modern anatase form.

Let me share what I know of the chemistry involved.

The iron in iron-gall ink comes from "green vitriol" or iron(II) sulfate FeSO4, a soluble clear light-green crystalline material.  Historically, it and "blue vitriol" (copper sulfate, CuSO4) were collected from old iron and copper mines whose ores were sulfides of the metals (pyrite, chalcopyrite, bornite, etc.).  Water with dissolved oxygen percolating through the rocks turned those sulfide minerals into sulfates.  Sometimes that water pooled on the floor of the mines and evaporated, leaving crystals of the sulfates behind.  ("vitriol" comes from the Latin for "small glass").

Ferrous sulfate can also be made by dissolving iron or steel metal (but not iron ore or rust) with sulfuric acid.  By 1400 European alchemists had already learned how to make sulfuric acid; but the usual process was distilling it from green or blue vitriol.  Thus I don't think it was normally used to make green vitriol for iron-gall ink.

But, either way, green vitriol should not contain significant amounts of titanium, because the process that formed it from sulfide ores would not form any soluble salt of titanium. In fact titanium salts easily decompose to form titanium oxide and other insoluble compounds.  Anyway the pooling and crystallization of the green vitriol would tend to exclude impurities, either solid or soluble.  

Thus iron-gall ink should not contain any significant amounts of titanium.

The titanium that was detected in the Vinland Map was titanium dioxide TiO2 in a specific crystalline form (anatase) that began to be produced synthetically in the early 1900s.   It is a white insoluble pigment, but the crystals are so small that they stay in suspension in usual ink formulas, like the fat droplets in milk.  

Colored inks and paints can be made from soluble dyes or from solid pigments.  The former produce transparent films whose hue changes with thickness in a characteristic way. Like, "yellow" dye ink would change from colorless to light greenish yellow to golden yellow to orange to red and ultimately to black.  Moreover, if the substrate is colored, its color will show through the ink or paint.  In particular, if the substrate is black, the result will look black, no matter how thin or thick the coat is.

Inks and paints based on insoluble pigments, such as tempera and watercolor, instead form semi-transparent or opaque films whose color depends on thickness in a very different way.  Like, red watercolor will change from colorless to pastel pink to full red, when the surface is entirely coated with the pigment particles; and then will remain the same red color no matter how thickly it is over-painted.  And while the color of the substrate will show though thin films, the saturated color will be the same on any substrate, including black.

For those reasons, solid pigment inks are generally better for art and writing than soluble dye ones.  But they are expensive to produce, since each color comes from a specific mineral that, even when produced synthetically, must be ground and sifted to obtain grains of the required small size.  Today, common opaque inks and paints are often based on soluble dyes with titanium white added.  This makes them behave like solid pigment inks. Namely,  when the thickness of the paint or ink exceeds a certain point, the painted surface will be entirely covered by titanium white particles coated with a layer of dye with fixed thickness -- hence with a fixed color.

On the Vinland map, the titanium white was probably added by the forger to his ink formula in order to make the traces and/or their "halos" come out with the right hue and opacity.  

But while McCrone detected some titanium in the X-ray fluorescence spectrum in some particles of two samples of VMS text ink (17 and 20), the X-ray diffraction spectrum saw no sign of titanium white.  The former technique only detects which elements are present, with no information about their chemical state.  The latter measures the spacings and angles of atom layers in crystalline materials, which can identify crystalline pigments (such as azurite or titanium white).  

Neither method can positively identify iron-gall ink.  Instead, it seems that McCrone goes by elimination: if it it is dark writing ink, has iron, but has no crystalline pigment, they would say "iron-gall ink".  This is normally a safe bet, because the only reason to write something on vellum instead of paper was the desire to make it water- and wear-resistant for many decades; which could only be achieved by writing in iron-gall ink. 

This deduction is so dependable that, when McCrone examines dark writing ink and finds has no crystalline pigment and no iron, they will say ... duh ... "iron-free iron-gall ink".

The honest thing would be for them to say instead "iron-containing" (or "iron-free") "dark ink of indeterminate composition".  But that would not look good on the report, would it?

And in fact there are many signs that the VMS text and drawing ink was not iron-gall ink.  It does not seem to have any of the properties that made iron-gall ink the only right choice for writing on vellum.  Including its color in the infrared scans...

An that could explain why McCrone detected titanium, but not titanium white, in sample 17.  If the ink is not iron-gall, the most plausible alternative is an ink based on some common insoluble brown pigment, such as sienna or roasted ocher, with a binder like gum arabic.  Unlike green vitriol, these minerals often contain titanium as impurity.  Such an ink would have all the "qualities" that we can see in the VMS: brown color instead of purple-black, wears off easily, washes off completely even after many decades, is transparent to 950 nm infrared light...

All the best, --stolfi

(30-10-2025, 03:08 PM)Jorge_Stolfi Wrote: You are not allowed to view links. Register or Login to view.Let me share what I know of the chemistry involved. 
 ...   
that could explain why McCrone detected titanium, but not titanium white, in sample 17. ...

Jorge, your detailed description is very helpful. If I understand correctly though, you are suggesting that the presence of titanium is consistent with a pre-modern ink based on natural brown pigments (like sienna or roasted ocher) rather than iron-gall ink, because these minerals may often contain titanium as an impurity. That theory would indeed account for the element's presence without implying modern materials like synthetic titanium white.

You are correct that the McCrone analysis seems to have seen no titanium white. And the distinction  is indeed crucial –  titanium white is titanium dioxide (TiO2) in a specific crystalline form (anatase), which, when synthetic, suggests a post-1900s origin as it did with the Vinland Map. 

But the McCrone report states "Titanium compound" for Sample 20 and "Titanium compound (particle)" for Sample 17.
Generalizing that finding as a common impurity minimizes the analytical weight given by the report's language and it ignores the expected protocols of a report from a professional source like McCrone.  They were specific in their terminology.  As one expects in a report from a professional laboratory like McCrone, they use explicit qualifiers when constituents are present at low levels, such as "Iron gall ink (very low iron)" , "Cuprite (minor)", or "Azurite and cuprite (traces)", etc. The fact that the McCrone report listed "Titanium compound" for Samples 17 and 20 without any such qualifier (like "trace" or "minor") strongly suggests that the titanium was present at a concentration deemed significant and measurable by professional analysts.

We have to acknowledge that the McCrone report explicitly identified a "Titanium compound," which, despite not being identified as (and likely not being) a specific crystalline form of "titanium white" raises a distinct inconsistency with the expectations of a medieval source for the pigment. (Attempts to get an explanation for this inconsistency from McCrone and other sources at Beinecke have failed).

I know that others have also attempted to claim the presence of this titanium as a common, insignificant impurity, but it seems to be driven more by a desire to explain away the element rather than to treat the evidence objectively. The analytical fact of a significant, unqualified "Titanium compound" finding has to be addressed without being generalized away.

(30-10-2025, 11:33 PM)asteckley Wrote: You are not allowed to view links. Register or Login to view.But the McCrone report states "Titanium compound" for Sample 20 and "Titanium compound (particle)" for Sample 17.
Generalizing that finding as a common impurity minimizes the analytical weight given by the report's language and it ignores the expected protocols of a report from a professional source like McCrone.  They were specific in their terminology.  As one expects in a report from a professional laboratory like McCrone, they use explicit qualifiers when constituents are present at low levels, such as "Iron gall ink (very low iron)" , "Cuprite (minor)", or "Azurite and cuprite (traces)", etc. The fact that the McCrone report listed "Titanium compound" for Samples 17 and 20 without any such qualifier (like "trace" or "minor") strongly suggests that the titanium was present at a concentration deemed significant and measurable by professional analysts.

We have to acknowledge that the McCrone report explicitly identified a "Titanium compound," which, despite not being identified as (and likely not being) a specific crystalline form of "titanium white" raises a distinct inconsistency with the expectations of a medieval source for the pigment. (Attempts to get an explanation for this inconsistency from McCrone and other sources at Beinecke have failed).

I have read the McCrone report, and must say that I don't share your respect for their competence in interpreting and describing the results of their tests.

The report has four EDS spectra of sample 17.  EDS ("Energy Dispersive Spectroscopy") works by measuring the X-ray fluorescence emitted by the sample when hit by the electron beam of a scanning electron microscope.  Thus it can reveal the elements (but not the compounds) present at each spot of the sample.

According to Table I, sample 17 is "black ink from drawing (woman's face)" from page f70v.
Not clear whether that was from what I consider original drawing, restoration round 1, or retouching rounds 2 and 3. (Probably they picked the darkest ink, which would be my round 3). 

They collected two other samples of the "black" ink, 13 from the text and 14 from the drawing, both on f80v; and those had no sign of titanium.  They also collected samples of the "black" ink from You are not allowed to view links. Register or Login to view. (16), from the folio number of You are not allowed to view links. Register or Login to view. (15), from the quire mark on You are not allowed to view links. Register or Login to view. (19), and from the "a" in the right margin of You are not allowed to view links. Register or Login to view. (20).  Sample 20 is the only one of these that showed any titanium.  But all these writings are known to be much later than the original writing.

It does not help that they mix up "folio" and "page", and call "black" ink that is actually various shades of brown. It does not help either that they totally fail to mention the large variations in ink density and color across the VMS, which would at least deserve a short explanation for why they did not consider it worth sampling and comparing them.

The report includes four spot spectra of sample 17, and only two of them shows definite signs of titanium.  Their interpretations of spectra 2/3 say 1.3/1.8% of titanium, compared to 5.7/5.8% of iron, 2.3/2.1% of copper, 2.9/2.9% of mercury, 0.9/0.0% of arsenic, and 0.5/0.5% of phosphorus; the rest being common elements that could have come from the vellum, binder, or dirt.  Thus only some particles in that sample seem to contain any measurable amount of titanium, and even then in only small amounts. 

Needless to say, titanium is present in those samples as compounds, not as the pure metal. So their use of the word "compound" means only that they cannot identify the chemical form.  And their data does not let one tell whether the only metal in the "compound" is titanium, or whether the compound could be, for instance, ilmenite FeTiO3, a fairly common black mineral that was occasionally used as black solid pigment.

  You are not allowed to view links. Register or Login to view.
  "Raman spectroscopic analysis of an important Visigothic historiated manuscript"
  "Of particular interest was sample AMS7, dated 1649–1662, where iron-gall ink was found mixed with another black pigment ilmenite (FeTiO3) [17]."
 
For spectrm 4 of sample 17, on the other hand, their interpretation gives tin Sn as 7.7%, more than iron 3.1%, copper 1.3%, and mercury 1.4% combined.  Tin is not an element that one expects to find in old pigments or inks (except maybe greens made by chemical processing of bronze scrap).  However, in the spectrum itself the peak labeled Sn coincides with a large peak also labeled Ca (calcium), which probably comes from the chalk paste usually applied to vellum in order to make it smoother and more receptive to ink.  So the 7.7% of tin may well be just an error of of the software that interprets the spectrum as a mixture of elements spectra.

Another one of the many things in the report that spoils my confidence in them is their claim of "palmierite" being detected in sample 8 (red-brown paint from the root of f26r). This statement is based onthe X-ray diffraction (XRD) spectrum, that depends on the spacing and angles of atoms in a crystal.  To identify a mineral, the spectrum is automatically compared to a large library of spectra, and the best match is taken to be the mineral present.

But palmierite, a sulfate of lead and potassium K2Pb(SO4)2, is an extremely rare colorless mineral found as tiny grains in the deposits around the fumaroles of Mount Vesuvius and a few other volcanoes worldwide, mixed with several other minerals.  It may be theoretically possible that pamierite formed over time from reactions between the red lead pigments used in the paint; or that the pigment used in the root was produced by a chemical process that happened to create some palmierite.  But what most probably happened is that the software McCrone used to identify the patterns from X-ray diffraction data found that the palmierite one happened to match the observed spectrum better than that of the mineral or mineral mixture actually present in the sample.  The technician just copy-pasted "palmierite" from the program's output, without bothering to check what "palmierite" was.  I bet he would have done the same if the output was "technetium perxenate"...

All the best, --stolfi

(31-10-2025, 11:31 AM)Jorge_Stolfi Wrote: You are not allowed to view links. Register or Login to view.I have read the McCrone report, and must say that I don't share your respect for their competence in interpreting and describing the results of their tests...

Excellent dissection of the McCrone's report -- Thank you for it. I see no reason to doubt your analysis.  
So much for "trusting the experts" though! 
 
I've expressed doubts on McCrone's competency in the past, but for other reasons -- mentioning Titanium in any form without elaborating to explain its precense, given their own history with and awareness of the Vinland map fiasco, is a glaring deficiency in their report for the VMS.

But if we believe they fell short as much as you describe, then we can't at the same time rely on their analysis to provide support for the claim that the ink and paint is consistent with a medieval origin.  Either the analysis by these "experts" is reliable, in which case there is a "Titanic Problem" with the VMS. Or it is not, in which case the 2009 McCrone report cannot be said to support any hypotheses on the dating the manuscript. We can't have it both ways.

(31-10-2025, 04:04 PM)asteckley Wrote: You are not allowed to view links. Register or Login to view.But if we believe they fell short as much as you describe, then we can't at the same time rely on their analysis to provide support for the claim that the ink and paint is consistent with a medieval origin.

"Consistent with a medieval origin" means only that they did not find any evidence of a more recent origin.  And indeed I cannot see any such thing in their raw data.

But they did not find any evidence that it is of medieval origin, either.   

In that direction, AFAIK so far we have only the C14 test (not in this McCrone report) that proves that the vellum was made in the 1400s. Is there anything else? 

We have Marci's letter, but some are disputing its authenticity.  Even if it is genuine (which I think it is) and the book it was attached to when it was sent to Kircher is the VMS (which I am assuming its, but can't think of a conclusive argument for), that still leaves the possibility that the VMS was written anytime between 1430 and 1600, using vellum made in the 1400s, before it was obtained by Baresh. Or maybe even by Baresh himself...

All the best, --stolfi