1) It's my understanding that Palagems first alerted people about the problems with these gems by firing off a warning to buyers through their newsletter. They then supplied labs in the U.S. with some samples to test, is this correct?
According to our data, the stones were first sent to labs and then Palagems later posted an alert.
We received the following forwarded e-mail originating from B. L., which was sent to a dealer in Bangkok on the 8th of January 2002. This was accompanied by indication saying it had also been forwarded to the GIA and AGTA):
" … I have given the 27!! pads purchased in Bangkok to GIA identification and research…AGTA is said to be certifying them as defused…! I believe the explanation is that the pinks are heated to a high enough level that the oxygen diffuses into the pink as an orange-layer component .. the technology is about to bring the treated-colored-stone business to it knees…! See you on the 24th Hope to have definite GIA reports by then.. B.."
An
AGTA Urgent gemstone alert dated January 3 (2002) Said:
"Sapphires With Near -Surface Orange Coloration. ……Initial observations on eleven gemstones show that the orange color produced is limited to a wide rim that follows the three-dimensional shape of the faceted gemstone, with the center of stone being pink.....
Further investigations are now being carried out to discover if (1) these stones are typical, or not, of similar orange sapphires presently being sold in Bangkok, (2) what specific process is being used to cause this near-surface coloration, and (3) if this near-surface coloration is stable (end of quote).
An
AGTA Orange-Pink Sapphire Alert followed on the 8th January, 2002, under the title
'Pink sapphires with an artificially diffused orange color at or near their surface and more details'.
Palagems website posted their observations on the 9th of January, one day after AGTA, and then updated them on January 11th, 2002.
In addition to preliminary research, GRS issued the first warning on 20th December 2001 and wrote, along with other information (quoted):
It is believed to the present knowledge of GRS (December 2001) that colors are stable and that only heat methods are used for this type of treatment. GRS checks the source of the new material of the next month...
...Sapphires with near-surface orange coloration have been reported from elsewhere. GRS will follow up the appearance of such materials and will include new on its own research on this topic in this page...
...The client should carefully examine its risks and the liability and the reputation of its supplier in addition to the tests made by GRS.....
A Summary of the observations and different colors was included in the form of a detailed chart (
see Appendix). GRS was therefore the first laboratory in the world to warn clients about this new treatment, however, this warning relates to the question of whether the colors are stable or not, as we could not exclude any long-term non-stability of these colors.
Our pioneering website publication enabled other labs to become aware of this new treatment and make their own contributions.
The quotations above - including our warning - has been legally notified and was deposited at a Lawyer's office in Bangkok (Thailand) in December 2001, copyrighted (in the USA) and evidenced in Switzerland by several client witnesses. We did this as we thought it essential to prove at a later date that we were careful to inform our clients about this new treatment.
2.) Did you first learn about these gems through Palagems?
No, we collected a large series of research samples on 14th December 2001 in Chantaburi (Thailand) after a client informed us that a new treatment was on the market and the first samples arrived in our laboratory in November 2001.
3.) How did you get a hold of samples?
We traveled to Chantaburi on the 14th of December and checked the material arriving from the heating factory in a dealer's office. We couldn't get actual access to the heating factories, so we parceled mixed research samples and sent them for heating to Chantaburi from a dealer in Bangkok. Heat-treating experiments were only officially carried out for us since Feb. 2002 after the Alert from AGTA was issued (Further details can be found in our journal '
Contributions to Gemology No.1' on this topic).
4.) For several months, there were many tests in different labs around the world. Could you explain to me what you initially thought it was?
On the 2nd of February 2002, we summarized our research in an interview given to the TGJTA (posted on the Internet, Copyrighted in Thailand and the USA).
The only changes that could be measured by a combination of ED-XRF and UV-VIS-NIR special testing were a change in the Oxidation State of Iron. (In analogy to: Schmetzer K., Bosshard G. and Hanni H.A.(1983): Naturally coloured and treated yellow and orange-brown sapphires. Journal of Gemmology 18: 607-622.)
We informed our clients on our website on December 20th, 2001, that this is not a traditional diffusion treatment as described in Kane R.E., Kammerling R.C., Koivula J.I., Shigley J.E. and Fritsch E. (1990): The identification of blue diffusion-treated sapphires, published in Gems and Gemology but more of the type published in Eigenmann (1970), Dissertation Nr. 4552, Swiss Federal Institute of Technology, with changes in time, temperature, pressure and variation in gas conditions during the experiments.
However, we very clearly stated the status of our research in a interview to the TGJTA on 2nd of February, 2002, which was also posted on our website (copyrighted and multiple evidenced):
quoted:
" TGJTA Question No. 4: Scientifically an not in trade terms, do you think that they are any chemicals added like in the diffusion process?
GRS answer to TGJTA: The current research on the trace elements Fe, Cr, Ti seems to be resolved in the way that these elements are not diffused into the heat enhanced sapphires by the new method. From this point of view, there is no prove for a diffusion process involved. The discussion is at the moment concentrated on lighter elements such as Magnesium (Mg) and others and whether there is any kind of other elements diffused into the sapphires. Unfortunately, some of these elements are relatively difficult to measure at very low concentrations by non destructive methods. The final debate seems to be concentrated in this corner of the research. GRS believes to be able to present its final research within acouple of weeks to the gemological world. Although it is currently believed that a diffusion process (in the established sense of the gemological literature) is not involved, we are desperately trying to find other element zonings in the stone. The information and eventual alerts will be published on our project web site (www.padparadscha.info)." End of quote
5.) Did you change your mind after further study?
Our study was completed in May 2002 and trademark procedures filed in July 2002 in the USA. It concluded as (Status June 2002):
Enhanced by heat (E) and diffusion inducing color zoning by internal (I) migration (M) of trace elements and defects, and formation of color centers.
Our studies confirmed the GIA's findings of Beryllium in the stones. We went through the same experience as the GIA. As the extremely costly machinery needed to measure Beryllium is not commonly available to gemological laboratories, we used the LA-ICP-MS laboratory at the Swiss Federal Institute of Technology. GRS, together with Prof. Dr. D. Günther, was the first laboratory to successfully measure Beryllium with this method worldwide. The attempts of GIA to measure Beryllium with LA-ICP-MS were not successful (see GIA Publication, GIA Insider, Friday 15 February, 2002).
This shows that even GRS' pioneer work was necessary before Beryllium could be found with this method. These difficulties gave a delay of 1-2 months for the final assessments. It is therefore not a change in opinion, but down to the difficulty in measuring light elements (Beryllium) at a level of only 0.001%.
We refer to the GIA publication Loupe Vol. 11. No. 2 (Spring, 2002), Page 12. Researcher Reveals Preliminary Findings Treatments. Rim effect in Thai rubies and Madagascar sapphires points to diffusion.
quote:
"The study also included chemical analysis of the treated stones. Using equipment commonly found in major gemological laboratories, GIA researchers determined there was essentially no chemical difference between stones' inner material and the rim. However, after utilizing more sophisticated instrumentation- Secondary Ion Mass Spectrometry, or SIMS- it was concluded that the orange/yellow rim contained a higher concentration of beryllium. SIMS is capable of detecting very light elements at very low concentrations that other analytical methods cannot detect" (end of quote)
6.) How would you describe the treatment given to these stones?
On the 20th of November 2002:
. Natural Fancy Sapphire
.
Enhanced by heat and light elements (if
present: inducing color zoning with orange rim).
. In addition giving our full research article:
http://www. gemresearch.ch/journal/E-IM.htm
7.) Is your assessment of the stones different form others in the field?
Our assessment is not much different, however we have proposed a new name for this treatment as we think this type of treatment is completely new and it therefore deserves a new name. After posting a suggested name on our website and collecting responses, we then proposed the name to the industry. Any solution that is accepted by all parts of the industry, including the end consumer and the producers, and which also fetches the consensus of the large majority of other laboratories' conclusions, will be carefully investigated and, if not in disagreement with our research, will be adapted.
We agree with the GIA's on-line publication when they state (quote)
"the results of their investigation strongly suggests that Beryllium is not the direct cause of the surface-related orange color layers and it is possible that the diffusion of Beryllium and perhaps other elements into the stone may be creating a reaction with the inherent chemistry in the corundum that gives rise to the yellow to orange coloration" (end of quote) (
GIA internet publication Volume 4, Issue 10, May 2002).
We agree with
GIA Publication Volume 4, Issue 3, January 28th 2002 Elaborating on the differences in the new treatment against conventional surface diffusion treatment:
Quote:
"Although the near-surface, facet-related orange layer in many of these stones is very similar to the type of color-zoning seen previously in diffusion-treated stones, we observed none of the other identifying characteristics of diffusion: There was no higher relief in immersion, patchy surface color, or concentration of color at facet junctions…. We observed no change in the color appearance of the test samples…. (continued) At this time, however, we question whether this new treatment should be classified in the same category as the surface diffusion-treated stones we reported on in the past. If only for the sake of the numerous dissimilarities between the two, it may be necessary to separate them in some manner. We do not believe we have enough information at this time to make that judgment. … (text continued) .. Regardless of the actual mechanism involved, proper disclosure of this treatment is essential. Such disclosure is complicated in this case by the extreme variability in the depth of penetration of the orange color, which in many cases would not be considered near surface. Until more information is available, GIA Gem Trade Laboratory identification reports will note in the comments section the nature of the color zoning in these stones, using notations such as " The orange color of this stone is confined to a near-surface layer". (end of quote).
We agree with
GIA publication February 15, 2002 (Volume 4, Issue 5).GIA Researcher Uncovers Important Data on New Treated Corundum - about the presence of Beryllium, but only accept it as qualitative data and we think that the data published is
not quantitatively correct (e.g. Al-concentrations are wrong).
We agree with the
Unified AGTA/GIA/Gueblin/
SSEF disclosure policy (February 25, 2002)
when they wrote:
Quote:
Why not the term "Diffusion Treated"?
None of the agreeing laboratories knows of a likely mechanism that could produce these visual effects or apparent differences in trace-element concentrations from the rim of the stone to the interior, other than diffusion of a chemical or chemicals into the surface of the stones. Nevertheless, as the trade usage of the term " diffusion" without any qualifier such as the inadvertent dropping of the word " surface" hence "surface diffusion" see CIBJO rules) has upon analysis, been found lacking both in terms of technical accuracy an descriptive purpose, it has been decided to remove this term from our report wording in relation to this treatment. (end of quote)
We agree with the GILC meeting with GAAJ, C. Milisenda, S. Kennedy and I. Eliezri regarding the statements made in the minutes of the Gemstone industry and Laboratory Conference in Munich (Germany), 21st, March, 2002, which summarized the following statements of the laboratories:
Quote:
"GAAJ Reports (Japan): The stones are disclosed as " enhanced" with the comments: " Different colors are found at the surface related layers of the stone induced by new technique of heating". At the moment reports are not issued.
K. Scarratt said that the AGTA-GTC is operating in accordance to the unified disclosure policy.
C. Milisenda said that the Idar-Oberstein Gem lab still issues their reports with " enhanced" or "heated" but not "treated".
GIT Lab has also stopped issuing reports non these orange sapphires.
C. Smith (GGL) explained that SSEF, GGL, AGTA, GIA declare these stones as "treated" and will not be called " Padparadscha". The description of the color can be slightly different.
L. Garcia-Gulllerminet (Lab. Francaise de Gemmologie) agrees with the "treated" statement.
S. Kennedy (GAGTL) stated that with the color being superficial a new form of treatment declaration must result.
I. Eliezri (President of ICA) remarked that these corundum are in any case natural stones."
(end of quote)
8.) Why are the distinctions between heat treatment and diffusion important to our business?
Surface-diffusion treated gemstones have a clearly established market place. Mostly blue sapphires with very shallow Ti diffusion near the surface are understood in the trade as Diffusion-treated sapphires. This type of materials has a clearly defined market value. In contrast, diffusion of light elements such as hydrogen is not a new aspect in the heat-treatment and has so far been accepted in the enhanced category:
We refer to the Gems & Gemology paper of Emmett and Douthit T.R. (1993): Heat Treating the Sapphires of Rock Creek, Montana, Gems & Gemology, Vol. 29, No. 4, p. 250-272.
Page 256 (Quote): The hydrogen partial pressure in the furnace is also important, because hydrogen atoms are so small that they can diffuse rapidly into sapphire and participate in solid-state chemical reactions…
Page 270: …. The incorporation of hydrogen into sapphire is another effect that merits discussion. When sapphire is heated in an atmosphere containing hydrogen, some hydrogen diffused into the stone and a portion of the H atoms will ionize into an electron and proton….. This creates an OH- molecular ion in the sapphire crystal… (end of quote)
In the past, this kind of treatment was categorized enhanced and had its own market value. New enhancements will have to be compared to these two different types of treatment. Diffusion of light elements in gemstones during the heating process is not sufficient for disclosing them as diffusion treated, because it is an accepted trade practice. The key is the exact nature of the color centers and the participation of the diffused elements in the color of the gemstone is a critical issue. This debate needs time to be resolved. The gemstones reacted very individually when exposed to the new treatment such as:
Cited from GIA research (
GIA internet publication Volume 4, Issue 10, May 2002).
(quote)
…However, we also have a pink stone that had a high level of Be near the surface, although it appears that the color was unaffected. In addition, an orange stone colored throughout showed higher Be in the center than the rim. It is possible that the color change in those stones that do react to the process may be due to a complex chemical reaction with the host corundum. Because different corundum have different chemistries, the results of the treatment are also variable…..(end of quote)
Our conclusion at this point is, that stones react individually and there are many possible causes of color origin.
This makes it so difficult to position this new treatment in either the "enhanced" or "treated" or "diffusion treated" category. This is why we proposed a new category.
We are presently checking the latest research on the nature of the origin of color in the new treatment through our own research.
9.) Do you have any idea how many of these stones came into the U.S. or European markets? Do you know what they were initially priced at? What should they be priced at based on your information?
We cannot answer these questions as we are not involved in the marketing, selling of these goods. We cannot also tell you how many stones entered the U.S. or European markets as we specialize in the certification of Burmese goods and other sapphires not enhanced by heat. We were also not approached by the trade to certify these newly treated stones in large numbers. Upon completing our research, it became even rarer for these goods to come to our laboratory.
10.) How often are you faced with such challenges? Are there many "tricks of the trade" developed by Thai dealers?
The arrival of new treatments using light elements received a very strong response from the laboratories in the sense that new testing instruments were introduced, such as LA-ICP-MS and SIMS. These instruments can be used in future research. Heat treating factories have varied ownership and can include individuals from many different nationalities. Therefore, to conclude, we should concentrate on firms, which are the responsible juristic persons, rather than countries in general.
11.) Are they getting better at treating stones?
The newest treatments included a variation of gas compositions (including Beryllium) as well as utilizing higher temperatures. A further innovation is expected in terms of changing another parameter: pressure. Our assessment is that the heating laboratories will always try to improve their techniques. GRS has consulted with heat-treating laboratories and suggested they make research papers and consumer information brochures first, before entering the market with new products.
20th November 2002
Dr. A. Peretti
GRS Gemresearch Swisslab AG
Lucerne
Switzerland
Explanation of the new treatment appearing in our website on December 2001
| Starting material |
Source (mining origin) |
Resulting color by adding yellow to orange color and reducing blue (purple) |
|
|
|
adding considerable orange (yellow) |
adding minor orange (yellow)* |
|
|
A |
B* |
| pink |
Madagascar, Sri Lanka |
orange |
Pastel Padparadscha |
|
|
|
Padparadscha Intermediate color |
|
| colorless |
Madagascar, Sri Lanka |
yellow to orange mixtures |
Pastel colors in yellow and orange |
|
| dark purple-red |
Thai, Africa, Madagascar |
orange-red (Intense Padparadscha) |
red |
| dark red |
Thai, Africa, Madagascar |
orangey-red |
vivid red |
| deep red |
Africa, Madagascar |
orangey-red |
vivid red |
|
| purplish-pink |
Madagascar |
orange |
Pastel to Intermediate Padparadscha |
| brownish-pink |
Madagascar |
orange |
Pastel to Intermediate Padparadscha |
