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Old July 19th, 2007, 11:50 PM   #1
SirRobertAnderson
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Default Let's discuss the Leeds Reports !

Here's something I posted awhile back on the Casebook, almost a year ago.

I will add that Lars rightfully pointed out problems with testing for N...but it's the Al that's the key here.

This ink ain't Diamine, and Mike Barrett doesn't know what ink it actually is, either.

My money's on Victorian Manuscript.

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Originally Posted by sirrobert View Post
Robert Smith and I believe the posting of two graphs from the Leeds reports will not set off an international copyright war. In a perfect world, I'd be able to post everything, but it's not a perfect world. Folks that want to obtain hard copies of the report are urged to get in touch with Mr. Smith.

Handwriting on the graphs is mine. Figure 1 is simply paper from the Diary; Figure 2 is the Diary ink plus paper.

As I have said, I am not a scientist nor do I play one on TV. But there appear to be some salient points to be discussed.

Chloroacetamide does not contain aluminum (Al). It does contain nitrogen (N). The converse seems to hold true for the Diary ink; i.e. you can see how Al spikes on the graph. I don't see any sign of N.

The Diary ink contains silicon (Si) and dramatically higher levels of sulphur (S). Now the silicon is intriguing as Lars has previously posted how Victorian "writing sand" contained hefty amounts of silicon and you will notice here how Si is in both the Diary paper as well as in the ink.
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Old July 20th, 2007, 02:38 AM   #2
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Hi ho

I cannot resist an ink discussion so lets have at it.

Recently, somewhere around here, I pointed out a reference where the presence of Al (among other things) was mentioned in the following context "Vitriol [Iron sulphate] is contaminated in varying percentages with salts mostly present as sulphates of copper, manganese, aluminum or zinc. These contaminants are characteristic for historic iron gall inks."
from:

Faubel et al, Non destructive analysis for the investigation of decomposition phenomena of historical manuscripts and prints, Spectrochimica Acta Part B, in press, july 2007.

The same authors present a SR-microXRF spectrum of an iron gall ink and the paper it is on from towards the end of the 18th century.

What bothers me is a number of things.

1. In the 1796 ink, there is a lot more present than in the Diary ink. There are a range of metals including Ca, Zn, Pb and Mn. No Al is found. Very few of these metals are in the Diary ink.

That is not to say that ink from 100 years later may not have been made better with respect to purity or that the iron sulphate used (which is the primary carrier for such impurities) may not have been different. But they are substantially different. Why one might get such metals in 18th century ink and not 19th, is, if I hazard a guess, because the vitriol used in the earlier ink was obtained by a different process which had progressed to a point where many of the contaminants could have been eliminated? Or a different source entirely?

You may find a history of "vitriol" (the component of iron gall ink we are interested in) and its production in Karpenko, V. and Norris, J.A, 2002, Vitriol In The History Of Chemistry, Chem. Listy 96, pp. 997-1005 but I warn you: its murderous reading.

2. The nature of the Fe and S relationship.

In the diary ink, if you notice, the Fe peak is small, the S peak is large, and so is the Al peak. In the 1796 document, the iron peak is much much larger relative to the S peak, and there is no Al. This is a bit confusing. If iron sulphate was present in the diary ink in the proportions indicative of iron gall one could argue that the relationship should be similar to that of the older ink.

But it isnt. That could of course be due to the set up's used or whatever. Or, in the Leeds diary ink, the large Al peak could indicate the presence of Al as a sulphate species contaminant, increasing the size of the S peak relative to the iron peak. Which would be indicative of Al present in the ink due to the iron sulphate having been obtained as a by product of the alum production industry?

Its all very confusing......but interesting nonetheless. As an excercise....

p
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Old July 20th, 2007, 04:19 AM   #3
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Hi ho Mr P,

Would you expect Dr Eastaugh, Bob Kurantz (Rendell's ink specialist) and Leeds University to have the combined expertise to recognise any significant inconsistencies with an iron gall ink of the late Victorian period?

They conducted their own analyses of the diary ink in 1992, 1993 and 1994 respectively, and none found any inconsistencies.

Love,

Caz
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Old July 20th, 2007, 05:01 AM   #4
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Hi ho Caroline Morris

You will of course have noticed that not once did I say anything or even comment on whether or not the Diary ink was resembling or not anything other than the ink for which I have seen a spectra.

Quote:
Would you expect Dr Eastaugh, Bob Kurantz (Rendell's ink specialist) and Leeds University to have the combined expertise to recognise any significant inconsistencies with an iron gall ink of the late Victorian period?
Why wouldnt I?

Quote:
They conducted their own analyses of the diary ink in 1992, 1993 and 1994 respectively, and none found any inconsistencies.
Never said they did. I think I'm missing the point here.....?

But of course one could ask the question (which isnt really here nor there) ....

Leeds say that the only major differences between the diary paper and the diary/ink combo is the presence of iron and an increased sulphur content.

No mention of Al. Which could mean, to my eyes, the Al is in the paper. And not the ink. They say that they see no difference re: Al between paper and paper/ink. Only iron and sulphur.

The only place their analysis of genuinely old ink and paper shows up Al is in one sample of 1887 paper. Not in the inks.

Its a pity the spectra for the old things werent included as it would be interesting to see them. They seem to have been included at some point but I cannot find them. The only spectra I see are for the Diary and Diamine.

Either way, more testing is the way to go........


p
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Old July 20th, 2007, 09:28 AM   #5
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A little more from the past....

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Originally Posted by sirrobert View Post
I mentioned some time ago I was going to ask someone connected to my company to look at the Leeds reports and weigh in. I got referred to a biochemist in Manchester ; here is his response. We'll call him Mank for now and I'll also mention that he (mercifully) knows nothing about the Ripper case nor the history of the Diary.

Mank sez :

".....The argument will have to stand or fall through the analysis of the ink. Before we go into that it is worth noting that you are unlikely to get any scientific rigorous person to definitively come down on either side of the fence. Science does not work like that, it is all to do with probabilities.In any scientific test one always starts with the assumption that two samples are the same and experiments are carried out to disprove this assumption. In this case we would start from the assumption that the ink used in the diary is the same as a modern ink and only when we can disprove that would be be able to say that there is evidence that the ink is not from a modern source. But even then there is still a margin of error that we may be wrong (which is what all those p values from statistical tests are all about). In purely scientific terms nothing is ever totally proved or disproved, just that the evidence stacks up so that the chance of the alternative hypothesis being correct is so small that it can all but be dismissed. In such an emotive and famous case as this I doubt if you would ever get any reputable scientist putting their reputation on the line, which is why the reports are full of caveats and careful wording.

One of the key points is to do with the labels of aluminium found in the samples. The argument that it is due to environmental contamination is interesting and begs the question how much aluminium is present as a pollutant in the atmosphere (from memory, not all that much). However, this can't be taken as evidence as one does not know where the diary has been stored over time (be it 120 years or 20 years). Aluminium is certainly present in both the paper and the ink sample, with substantially more aluminium in the paper+ink sample. If the aluminium was due to environmental contamination then one would expect similar levels in each sample (as the contamination would most likely be on the surface) unless for some reason the aluminium bound preferentially to the ink rather than the paper. From my (admitedly rather not up to date) knowledge of chemistry, although aluminium is quite a reactive metal on exposure to air it readily forms aluminium oxide (Al2O3) which tends to inhibit further reaction. Therefore this would suggest that the aluminium is an actual component of the ink.

A strong argument for the exclusion of a diamine type ink is the lack of sodium found in the diary samples. Diamine ink contains nigrosine dye (See Leeds 3).

The ink does seem well adhered to the paper which could be indicative of age, or of the properties of iron-gallotannate inks, or possibly or a forging method, possibly warming the paper to expel any excess moisture from the ink and promote adherance (last point is pure supposition on my behalf, I have no idea what such a process would do to the paper and would also be likely to result in the loss of more volatile elements from the ink solution).

Considering that the evidence would suggest that the ink is of the iron-gallotannate type, one wonders why an extract was not attempted using dilute hydrochloric acid whcih would readily dissolve the ink providing a relatively paper-free sample.

One final point, the department at the University of Leeds which carried out the analysis has a very good reputation, as does the whole university, so I have no reason to suspect that the analyses were not carried out under the most rigorous conditions.... "
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Old July 21st, 2007, 04:13 AM   #6
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Hi ho posters

I have a full coffee cup so I'm going to wax lyrical.......

From Manks post (and ...no...I have no beef with him or his opinions and am typing in a congenial manner).

Quote:
The argument will have to stand or fall through the analysis of the ink.
...or the relationship between the ink and the paper which is more perhaps indicative of age or forgery method given the info we already know.
Quote:
In purely scientific terms nothing is ever totally proved or disproved, just that the evidence stacks up so that the chance of the alternative hypothesis being correct is so small that it can all but be dismissed.
Indeed. That is why the argument that we shouldnt get it tested unless that test gives a definitive answer is fundamentally flawed and a position that is hard to defend if one really wants to get to the truth.

Quote:
n such an emotive and famous case as this I doubt if you would ever get any reputable scientist putting their reputation on the line, which is why the reports are full of caveats and careful wording.
Indeed. Its a pity that much of that "emotion" arose from one camp who profess to want to get it tested and yet have worked hard to engender an atmosphere that is not conducive to achieving their stated aims.

Quote:
One of the key points is to do with the labels of <.................> inhibit further reaction. Therefore this would suggest that the aluminium is an actual component of the ink.
This is fair. There is no way that any level of ambient Al contamination in the environment is more than the amount of Fe present (as would have to be the case from the results) in the ink. Again, Leeds do not state in their conclusions that there is more Al in the ink/paper combo than in the paper alone.

Quote:
he ink does seem well adhered to the paper which could be indicative of age, or of the properties of iron-gallotannate inks, or possibly or a forging method, possibly warming the paper to expel any excess moisture from the ink and promote adherance (last point is pure supposition on my behalf, I have no idea what such a process would do to the paper and would also be likely to result in the loss of more volatile elements from the ink solution).
My understanding is that it is chemical reactions that cause iron gall ink to "bite" ? The same amount of moisture will be expunged by heating it for an hour as will be by its standing in a warm room for a day. When its dry, its dry. It doesnt matter how it gets dry.

Indeed, iron gall ink and its components react with cellulose in paper in a fairly well known way. That reaction progresses over time, producing changes in the cellulose and in the metal of the ink. It is those reactions and changes in both ink and paper that are less easy to simulate and which is why it is an analysis of the ink/paper and not the ink alone that will provide an answer.

Quote:
One final point, the department at the University of Leeds which carried out the analysis has a very good reputation, as does the whole university, so I have no reason to suspect that the analyses were not carried out under the most rigorous conditions.... "
They certainly do and it is only a fool of the highest caliber who would say that they "bungled" anything. But........their expertise lies in the analysis of ink, not necessarily in the analysis of ink on paper reactions.

Regarding Manks description of the scientific method....an interesting analogy is now coming.

Two years ago I got a beautiful root canal done, with a delightful (in appearance, not the experience or price) post and crown. recently however I have been waking up at night trying to claw my face off with a pain in what appears to be the tooth but which should be physically impossible.

I went to my dentist and he performed the tests that are available - x-rays, tappping, application of pain inducing liqours with malefic intent and so on.

he could not confirm it was the tooth based on these tests. he sent me further and two more dentists applied similar tests and still could not decide. Eventually I got to an endodontist who applied the same tests and was able to say that based on the other dentists work and the fact that she had seen perhaps 1000 such tests over her career, it was that tooth with 90% probability and that one root had not been fully filled and was causing a problem.

Not one individual dentist would say something absolutely definitive but a consensus gradually arise based on tests that individually are not conclusive and eventually a decision is made based on cumulative, individually non definitive tests and the experience of the operators.

That is why the document should not be analysed by people who may be technically proficient in such tests but by people who have seen thousands of iron gall documents, who work day in and day out with old and artificially aged documents (for conservation purposes) and who can bring that experience to bear on the problem in a way that perhaps other operators cannot.

A GP can do the same tests as an oncologist but if you want a diagnosis of your childs cancer, you go to the oncologist and preferably the one who has seen and interpreted as many test results as possible as they will have the most experience and can provide insights that the GP or a less experienced oncologist cannot.

If the cellulose fibres of the diary under the writing were analysed by the usual methods for their corrosion state for example by a group who had seen such analyses for 100's of documents: the result will not be conclusive for the age but equally the diary is being put in the same context as many other possibly old documents and the analysts can say whether or not they think the state of corrosion that is present could have been achieved by fraudulent means.

And they can do that because they are regularly and systematically artificially aging such documents to test the effectiveness of their conservation procedures.

If (hypothetically speaking!) it was found that the cellulose degradation (SEM or FTIR methods) as a result of the ink was similar to to other old documents they had seen and not similar to artificially aged documents they had seen, one knows that either the ink is on the paper a long time or the forger had access to artificial aging methods that they did not.

And this result is added to all the rest and so on and so forth until eventually, the probhability of the ink being either old or new reduces for one of them.

One has to remember: document conservationists are the best forgers....they have to be as they cannot be messing around with George Washingtons laundry bill or whatever.

Not only will such characters be able to look at the diary as possibly an old document but also will be able to look at it for signs that it was forged (And they should know them).

The scientists that have been approached so far have not it seems belonged to such a group and who would appear to be the only logical people with the necessary skills.

p
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Old July 21st, 2007, 08:31 AM   #7
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Lars, nice to see that experience and judgment still have a place in the mathematical and computerised realms of physics and chemistry.

Robert
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Old July 21st, 2007, 04:58 PM   #8
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Quote:
Originally Posted by Mr. Poster View Post
Hi ho posters

I have a full coffee cup so I'm going to wax lyrical.......

From Manks post (and ...no...I have no beef with him or his opinions and am typing in a congenial manner).
And Dr Mank returns the respect and mad love back at ya.

He sez :


His (Lars) posting is nicely put. Most investigative trials are performed against a known standard or bench mark. The ideal situation would be a comparison with a verifiable document using the same or essentially similar ink/paper combination from a known source whose provenance is undisputed. Scientific tests can tell us what the situation is at the time of the analysis but there are all sorts of reactions that could have happened over the years that one may not be aware of or even consider. Of course, even such a comparison is not foolproof as a lot would depend on storage conditions etc. But it would be a better comparison and would have an effect on the balance of probabilities as to originality/forgery.

One point that probably needs clarification:

Indeed, iron gall ink and its components react with cellulose in paper in a fairly well known way. That reaction progresses over time, producing changes in the cellulose and in the metal of the ink.

Cellulose is an organic molecule and will change over time, breaking down or being transformed into new molecules. However there will be no change to any metal which are elemental and cannot be changed (unless they were unstable radioactive metals!). The salt of the metal may change, although that wouldn't be possible to identify from the traces in the Leeds report, as well as the concentration. I presume that is what was meant rather than a physical change in the actual metal, but though that is was worth clarifying as the changes in cellulose and metal would be of fundamentally different types.

The point about using experts is a good one, it obviously makes perfect sense to see a specialist about a problem that they have a great deal of experience in. However, once caveat, even experts in the same field have differences of opinion often coming to their opposing opinions using the same evidence!

Dr. Mank


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Old July 22nd, 2007, 03:33 AM   #9
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Hi ho Posters

I have no quarrel with Dr Mank at all (strange how careful one gets on Maybrick threads) but I will tidy up this point:

Quote:
One point that probably needs clarification:

From me: Indeed, iron gall ink and its components react with cellulose in paper in a fairly well known way. That reaction progresses over time, producing changes in the cellulose and in the metal of the ink.

Cellulose is an organic molecule and will change over time, breaking down or being transformed into new molecules. However there will be no change to any metal which are elemental and cannot be changed (unless they were unstable radioactive metals!). The salt of the metal may change, although that wouldn't be possible to identify from the traces in the Leeds report, as well as the concentration. I presume that is what was meant rather than a physical change in the actual metal, but though that is was worth clarifying as the changes in cellulose and metal would be of fundamentally different types.
This is interesting because the point I was trying to make is getting lost in my poor phrasing.

Cellulose does change with time entirely on its own I would imagine.

As to the metal, Dr Mank is correct as to radioactive decay but there is also, and this is very important, a potential for change in its (a metals) oxidation state and that is the one I am referring to.

Damage of cellulose paper by iron gall can arise in two ways (and this damage may be invisible to the naked eye but can be observed in cellulose fibres with SEM):

1. the acid components of the ink (H2SO4 in the main) directly attack the cellulose fibres hydrolytically,

2, Fe2+ residues, due to incomplete air oxidation of the original FeSO4, act as catalysts for oxidation of cellulose components by interacting with radical species to form, amongst other things, H2O2 or hydrogen peroxide.

This is the important bit coming: Fe2+ acts as a true catalyst in the formation of the radicals and is neither changed nor altered in amount of speciation.

However in the forming of the peroxide species by a series of fairly well characetrised reactions known as the Fenton Reaction, Fe2+ can be oxidised to Fe3+ which is a different kettle of fish.

These reactions and the interaction of ink and cellulose in this form are well documented and I can provide information to anyone who wants it. A useful reference being: B. Reißland, Ink corrosion: aqueous and non-aqueous treatments of paper objects—state of the art, Restorator 20 (1999), pp. 167–180.

So theoretically, I was correct to say the metal can change: admittedly its a change in oxidation state but to a chemist at least, a change in oxidation state is a change in the properties of the metal such that th etwo species can be regarded chemically as fairly distinct.

This Fe2+/Fe3+ ratio produced by these reactions has, in recent years, become a "new" tool in characterising inks and paper and the potential for degradation.

If all the Fe2+ is gone, one can assume that the damage potential to the paper is over as the first reaction cannot occur anymore.

If there is lots of Fe2+ present, then the potential for further damage is still present.

The methods involve "mapping" of ratios across individual ink stains or lines and looking at the spatial distribution of the relative amounts of these species throughout the ink lines. And so on and so forth.....

Such things cannot data application of ink to paper. But in the same way that whilst an x-ray and tooth tapping cannot identify a failed root canal on their own but in the hands of a practiced dentist can be interpreted to an acceptable degree of confidence, perhaps such analyses, whilst not providing a date of application, may in the hands of someone with long experience, provide an indication.

No technical details, or specs, or method descriptions will say that "micro-XANES Mapping of Fe oxidation states" will data ink but an experienced practitioner could easily say "I cannot date it but Ive only ever seen that pattern in artificially aged documents" or "Ive only ever seen that pattern in genuinely old samples" in the same way that a mammogram cannot tell if a tumour is benign or malignant but an experienced mammographer may be able to say "I cannot say for definite but Ive only ever seen that particular type of mammogram in malignant tumours" or can infer something more from subtelties of the results.

Now I know Caz is going to start on about "Oh we need a definitive test" but for a thousand reasons ranging from professional responsibilities of the analyst all the way down to Heisenberg uncertainties, that is never going to happen.

But Id accept the results of a non-definitive test conducted by a professional who's bread and butter (and if he's doing the job at that level, its probably his passion as well) is the analysis of the problem to hand rather than the results of a white-coat down th eroad who was selected for convenience sake.

regarding point 1 above, the hydrolytic attack of celluose fibres by acids in the ink: it would be very nice indeed to hear an expert opinion on whether the diary fibres exhibit a degree of degradation consistent with a hundred years of reaction or more consistent with 20 years of reaction and if such a difference could be engineered artificially.

As Ive said before, my personal opinion is that it is the relationship between ink and paper that will give clues, not further analysis of the ink (unless of course we just want to lay the chloroacetamide issue to bed).

One aspect of the ink that could be worth looking at is the organic constituents. Techniques exist today to determine the binding agents (Gum Arabic, egg white etc.) of an ink. It would be interesting maybe to go down that route as perhaps some binding agents are more indicative of age than others? But thats just hypothesising.

P
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Old July 22nd, 2007, 02:19 PM   #10
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And Dr. Mank writes:


Moot point really changes of, for example, Fe2+ to Fe3+ may occur but it is still iron and it is the compound it forms with oxygen that has changed. That couldn't be determined by the type of analysis used. There are also different isotopes of many metals, for example Lithium-6 and Lithium-7, but both are called lithium (and it is notpracticably possible to change one to the other)

My point was for the lay reader if you mention that the 'metal has changed' it could conjure up images of alchemy. Lars is right that these are chemical subleties but I think it would take a lot of complex investigations, more than was done on the paper and ink, to determine the oxidative states that the metals are in. I certainly wasn't disagreeing with anything that Lars has written, just trying to make the often complex and puzzling ins and outs of chemistry a bit easier for the less scientifically minded!

Dr. Mank


Quote:
Originally Posted by Mr. Poster View Post

This is the important bit coming: Fe2+ acts as a true catalyst in the formation of the radicals and is neither changed nor altered in amount of speciation.

However in the forming of the peroxide species by a series of fairly well characetrised reactions known as the Fenton Reaction, Fe2+ can be oxidised to Fe3+ which is a different kettle of fish.
Very interesting, to put it mildly. Sounds like a promising angle to follow.

Wondering out loud: if the Diary was kept in storage at Battlecrease for a very long time, would those conditions influence the Fenton Reaction ?
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