@Kyarazen
Thank you again for providing your own analysis on the results.
I've been reading through your analysis of the GCMS, cross-checking the studies, and I have to say that doing so has only generated more questions for me.
In short, I still maintain my belief that 1985 is adulterated. I think there are too many question marks to reconcile and cross-contamination doesn’t explain enough of them away for me.
I’ll go through each doubt, point by point, below.
But first, I wanted to ask a couple of questions.
Do you now believe 1985 is an agarwood extract? What kind exactly?
I ask because people keep implying it is. What I remember regarding this, is your own position in the following two quotes:
From the original Kyarazen article:
"Pointing at the bottle, Mr Lee said, it was from 100kg of wood, distilled in 1985, a theoretical yield of at best under 1%."
And on Basenotes in 2013:
''it is definitely not solvent extracted as the solvent extraction process would generally give a hard brittle blob from high quality wood.''
http://www.basenotes.net/threads/400989-Agarwood-oil-thread-(Part-1)/page267
Has your thinking or information changed?
Regarding the question of 1985’s purity, what would it take for you to personally have suspicions?
Why don't you run a GC test of 1985 yourself? I believe you have the access and opportunity.
In any case, listed are my doubts regarding KZ85's purity:
1. The tester says the TIC number was very low, and that indicates that it has been cut with non-volatiles. What do you make of the very low TIC number? I don't believe you expounded on that.
if the aim was to "dilute or cut" an agarwood extract as this is, you will not see high percentages of Eudesmol, Aristolene, Valerianol, Guaic acetate etc. you might see these markers fall down to very low percentages as the cutting agent is increased. but so far, there is no major cutting agent present, and no cistus/labdanum compounds present... if any of these labdanum, benzoin, etc resins are present, it would have been obvious in the GC.
pthlates etc are commonly known to use to cut oils, but in logical sense.. whom would want to cut an oil by adding 0.7% only to it?! it would be 7%.... 70% even... but not everyone may have the same logical view.
Are phthalates the only way of cutting an oil?
The percentages are of the distribution of the volatiles, not of their total content within the sample. The point is, that non-volatiles won’t elute. I realise there is no definitive answer regarding any actual dilution level, that would require chemometric testing which hasn't been done. But in the absence of a concrete chemometric value, I can only rely on the tester’s evaluation.
2. Regarding the reference you mentioned for Valerenal:
http://iopscience.iop.org/article/10.1088/1757-899X/368/1/012023
There is no Valerenal detected in the study you linked to. Personally I’ve never come across any mention of valerenal in Aquilaria, let alone at such a high percentage of the total volatiles. If you manage to find valerenal in Aquilaria, please link to it.
3. You mention that you only found 5 unknown components in the results:
i personally flag out five of the components in red as they are not found in scientific literature to be known to be present in agarwood. in my opinion, either undiscovered yet or most probably a cross contamination from the facility especially without much standards/regulation in those days. it was known to be a
chinese medicine/herb extraction facility.
Personally I think 5 components is a significant number,
and in truth there are other unidentified components which you marked with grey. When I transcribed your analysis I marked them in red too, as in fairness they are hardly identified components.
Beyond the number of unknowns though, it is also a matter of their type. Besides obviously being atypical to agarwood, some of these compounds, to me, shouldn’t be in the sample, even if we accept unintentional cross-contamination.
4. Regarding the nitroquinoline compound:
http://www.ijtsrd.com/papers/ijtsrd8338.pdf
The compound is found in a methanol extract of Moringa oleifera roots from Nigeria. The peak is at a low 0.4%, and the peak is mixed, i.e shared by another 2 compounds.
Beside this citation, I've only found the nitroquinoline compound being sold by chemical companies. It seems more likely cross-contamination happened in the Moringa sample, or that it was from the (treated?) Nigerian soil, I still think it highly unlikely it is a plant derived compound.
I’m finding it hard to construct a scenario in which this ended up in a wild oud oil in such a high percentage by unintentional cross-contamination at a herbal extraction facility.
5. Regarding the aminoquinoline compound:
http://www.scielo.br/scielo.php?script=sci_arttext&pid=s0001-37652009000400011
The only 8-aminoquinoline listed in that study is primaquine, which is not a plant compound.
In fact, only quinine is plant derived, all the other compounds listed are synthetic analogues.
Again, I don’t understand how cross-contamination could have happened.
6. Regarding Carissone:
https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5815143/
There is no Carissone (11-hydroxy-eudesma-4-en-3-one) listed in the study,
the closest eudesmane sesquiterpene is 9-hydroxy-eudesma-3,11(13)-diene-12-methyl ester
which was found as a secondary metabolite in Sinensis that had gone through artificial holing.
Carissone is typically found as a secondary metabolite in Carissa edulis.
7.Regarding Cryptomeridiol:
http://pubs.rsc.org/en/content/articlelanding/1988/np/np9880500497/unauth#!divAbstract
The cited research does not say cryptomeridiol is a component of agarwood. Cryptomeridiol here is found in Amanoa oblongifolia, not in agarwood.
8. Regarding Chenopodiol:
http://krishikosh.egranth.ac.in/bitstream/1/5810011412/1/D-681.pdf
Chenopidiol was present as a constituent of essential oil from moderately infected Agarwood (Malaccensis), but not present in the highly infected sample.
9. Regarding Guaiol acetate:
http://citeseerx.ist.psu.edu/viewdoc/download?doi=10.1.1.878.1836&rep=rep1&type=pdf
Guaiol acetate was found in the extract from eaglewood offcuts vs the oud oil. Again, not high quality wood.
10. Aristolene:
From:
https://www.nature.com/articles/srep44406#f3
"agarwood sesquiterpenes (e.g. γ-eudesmol, agarospirol, aristolene) were formed only during fermentation of the resinous agarwood chips with Fusarium"
From: The volatile and semi-volatile constituents of agarwood, the infected heartwood of Aquilaria species: A review.
Aristolene is found in crassna 9yr plantation trees from Trat.
Not that it relates to purity, but it catches my interest and the thinking I have is, that aristolene comes from fungal infection, that wild high quality agarwood should have the effect of infection from the natural strain but not ever in a high percentage. The high percentage of aristolene, plus the general makeup of the 1985 oil make it suspect to me. Also, the presence of the sterols in the final oil I believe to be atypical of a natural wild wood. More likely the high percentage of sterols is due to the tree being in continual shock due to inducement.
11. You realise, of course, you are citing research results from Crassna, Agallocha, Sinensis, Malaccensis, and Gyrinops walla?
Citing results from methanol extraction, to headspace analysis, to microwave additional extraction?
Sourced from healthy wood, to offcuts, to artificially innoculated oud?
Where is the common thread?
Points 8-10, relate more to my own interest in the actual quality of the feedstock, but still, they do speak to the congruency of 1985’s story.
It is always possible to explain away a couple of doubtful points, but at what point do the doubts accumulate to the point that no explanation will do? It appears people were more focused on the labdanum aspect, and once the GC result confirmed the fact that it was not a labdanum adulterated/centered oil, all questions ceased. But in truth, questions remain, and I find it very hard to align all the data into a single congruent story. Personally, I think the data speaks volumes, and the conclusion is that 1985 is adulterated. The ‘how’ and ‘why’ hardly matter.
At this point, the only thing that could change my mind, would be a definitive (expensive) chemometric analysis of 1985, one that would disprove (doubtful) the findings of original report.
and the result of a GCMS is strongly affected by the column used, the temperature, and the solvent used, for example dichloromethane vs acetone gives two different populations and GCMS profiles.
For anyone who cares to know, the solvent used was dichloromethane.
with regards to the
gcms of the 1985, i thought i would come make a posting again.. albeit a more intellectual one just incase more people get caught up in the spiral and fall into different "camps" with different motives/motivations.
I couldn’t agree more.
I’ve kept to technical issues and that is all I’m interested in discussing.
I trust and respect Kyarazen, and can extend the same to Mr. Lee.
But that doesn’t mean I have to accept 1985 as pure.
In the case of purity, the problem (if you believe in one) would probably go back to the production site.
In any case, one must accept that we will never know the full story about KZ1985.