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Fakes & FraudsHow do they make fake Ametrine? Or is this real?
26th Mar 2015 21:17 UTCAlex
2nd image is a natural amethyst looking specimen I stumbled across but has the same dark concentrated purple tips. Is this fake too? Let me know what you think.
26th Mar 2015 21:51 UTCAlex Earl 🌟 Expert
Here is what the mindat Ametrine page says:
"While the purple sectors are made of amethyst, the yellow or orange sectors are not made of citrine, because they are colored by inclusions of iron compounds and would more properly called ferruginous quartz. Accordingly, upon heating ametrine the purple sectors pale, while the yellow-orange sectors keep their color. "
So the specimen could indeed be real, (although i am no expert), it looks as if the solution that formed the original quartz changed while the crystal was nearly done forming.
I am not going to address the "metaphysical properties", as i don't believe any mineral has any such properties. (no offence)
27th Mar 2015 02:04 UTCOwen Melfyn Lewis
As for the two photos, the first only has both the amethyst and citrine (pale) colouration.
Amethyst is formed when some colourless quartz, (containing appropriate Fe ions) is irradiated. This irradiation (gamma ray) can either be naturally caused or induced by man. Either way, this is the process by which amethyst gains its colour.
Some amethyst is altered to citrine by modest heating at 400-450 deg C. Citrine so caused is relatively lightly coloured (as in the first pic),. Such citrine can be made to revert to amethyst be exposure to gamma radiation. Alternatively, further heating of pale citrine at 500-550 deg C darkens the citrine to a golden-orange. Citrine of this colour can no longer be made to revert to amethyst colour by irradiation. Further heating of dark citrine at above 600 deg C turns dark citrine either colourless or milky (again not reversible).
In the growth of ametrine, the zoning of the amethyst and citrine follow distinctively different patterns in the natural and synthetic growths (see the above linked papers) with the growth of both occurring at the same temperature. The second link describes in some detail the scientific basis for the ametrine synthesisation method.
27th Mar 2015 05:24 UTCAlfredo Petrov Manager
In any case, when quoting any authorities from the literature on citrine, or reporting on experiments, it needs to be stated which of the two types of citrine is being referred to, otherwise the confusion just grows worse.
(Edit: This is rather an oversimplification of the classification of different types of citrine, because other types are possible too like quartz crystals with quartz colored yellow by microinclusins of ferric oxides ("Eisenkiesel" or "ferruginous quartz"), and one could also have different citrine mechanisms present in the same crystal.)
27th Mar 2015 08:15 UTCAlex
27th Mar 2015 12:16 UTCWayne Corwin
Ummm.. NOOOO They're NOT Alex !
One is true SCIENCE,,, the other is HOOOOEY !
Do we have to tell you which is which ?
;-)
27th Mar 2015 13:58 UTCDean Allum Expert
I do not understand your aversion to "Lab-Created" crystals. They grew on this earth too. In fact many generations of crystals ago, a natural crystal was the seed used to nucleate these crystals; that is, they have the same genealogy. The reason why the man-made quartz industry started was to create a reliable supply of large "perfect" crystals which have the desired Piezoelectric properties. If you have a watch or cell phone, then you are taking advantage of these crystals providing a heartbeat that they run by.
Just as in farming, there is a lab technician who intensely cares for these quartz crystals as they are growing and monitors their incubator to provide a loving environment for their growth.
Isn't crystalline perfection at the atomic level what you desire? Could you please provide some clarity on this issue? I feel that it is more than "just words" when people slander man-made crystals.
-Dean
27th Mar 2015 14:37 UTCOwen Melfyn Lewis
-------------------------------------------------------
> Confusion has been caused by using the term
> "citrine" for two different kinds of yellow
> quartz:
Alfredo, may we take this a step at a time and see where we can come together and what, if anything, will continue to hold us apart? If one allows ferruginous quartz (which, personally and in accordance to the view of Dr Nassau and others, I could never confuse with citrine), there would be three forms of yellow quartz: i.e. FQ, citrine and another yellow quartz, sometimes described as lemon quartz or honey quartz (now out of favour). Let's pick these apart as we go.
> One ("true" citrine) gets its colours from
> radiation-induced colour centers, is slightly
> dichroic, and loses its colour when heated.
I guess that what you refer to here is the 'lemon quartz'. Thus is a slightly greenish-yellow colouration in quartz, that sometimes occurs as a result of low temperature heating of smoky quartz (140-380 deg C, above which temperature this variety of quartz becomes colourless). Iron plays no part in this colouration but the nature of the colour centre responsible for this colour change is not (to my knowledge) yet definitively described. What is known is that this colour change on heating occurs in quartz containing no Fe but sufficient Al in substitution for Si to form smoky quartz when irradiated. The colour is stable to visible light but the colour change is reversible by gamma irradiation. Dichroism is commonly very weak, sometimes to undetectability. Lemon quartz is sometimes traded as citrine though, strictly speaking, it's best not to do so, because both the causes of its colour and the colour itself are not those of citrine.
> The other (including baked amethyst) gets its color
> from iron, is not dichroic at all, and does not
> lose its color on heating.
This is citrine as defined by Nassau and all other modern authorities, I think. One needs, perhaps to be more specific in that only amethyst containing Fe+++ produces citrine when heated. If the Fe is present as Fe++ then heating such amethyst at 400-500 deg C turns the purple amethyst to green (prasiolite). Please see the papers linked to in my post above to see how synthetic ametrine is formed by first growing synthetic citrine and then irradiating the grown crystal to revert the outer part of the crystal along clear crystallographic boundaries, to amethyst colour. Citrine also shows very weak dichroism and may sometimes be considered to show none.
Without chemical analysis, citrine is differentiated from lemon quartz by colour alone. In the chemist's lab, it is simple to differentiate lemon quartz from light or dark
citrine, because one can control exactly what goes into the soup out of which the crystals form. But nature is chaotic and in all probability in almost all geologically formed quartz both some Al and some Fe are likely to be present. In such a case it follows that amethyst forms where Fe-predominant Quartz is irradiated and smoky forms where Al is predominant. Between two 100% extremes, there must (in nature) be infinite degrees of random Fe/Al mixing so it's probably wise not to be too doctrinaire when considering crystals formed and coloured by some chance mix of processes.
> In my mind, at least,
> these differences are significant enough that two
> different names would be warranted, although we
> are stuck with the current imperfect terminology.
Here we agree, though for me with the caveats given above. I hope we might further agree as follows:
- In nature, the occurrence of citrine is fairly rare.
- Where amethyst is naturally found in abundance, citrine can be produced to order by heating amethyst to meet market demand for citrine. Because the crystalline forms of amethyst and citrine are identical and the heat treatment is essentially undetectable post-facto, this is the ideal method of augmenting the natural supply of mineralogical specimens of citrine to meet demand. Synthetic quartz is never likely to be presented as a natural mineral specimen because of different growth forms
- The bulk of citrine that reaches the retail market has been cut and polished and set into jewellery. Because of its relative lack of flaws, synthesised citrine is cheaper and easier to work well than is either naturally occurring citrine or that that is the product of heating natural amethyst. Thus, for citrine in jewellery made in the last 30-40 years and which appears either flawless or contains certain 'diagnostic' inclusions, such as the so-called 'nail-head spicules', there is a strong presumption that such material is of synthetic origin. Start by expecting 'synthetic' and examine carefully for any signs that discredit that assumption. If there are no such signs, then caveat emptor - and only pay accordingly.
- As for ferruginous quartz, though this is of interest to mineralogists, it is not considered to be a gemstone and should never be traded under the name of citrine. To do so would be as misplaced as would be (say) the selling of fuchsite-included colourless quartz as prasiolite.
28th Mar 2015 11:26 UTCDuncan Miller
We all know that quartz occurs naturally in various colours with varietal names – colourless rock crystal, yellow citrine, purple amethyst, pink rose quartz, brown smoky quartz, black morion, and the rare natural green prasiolite. Some of these colours can be produced artificially by radiation, sometimes coupled with heating. Artificial heating can also lighten some dark coloured quartz. Given the variations in natural quartz and their different reactions to irradiation and heating, a correspondingly wide range of artificial colours can be produced.
Most colourless natural quartz contains chemical impurities, even if these do not produce visible colour. They are mainly iron, in Fe-bearing quartz, and aluminium, in Al-bearing quartz. Natural or artificial irradiation with subsequent heating causes different colours in these two different quartz varieties.
First let’s consider Fe-bearing quartz. Naturally occurring clear Fe-bearing quartz crystals can experience low-level gamma irradiation from radioactive minerals in the surrounding rock. Over long periods of geological time this produces a change in the bonding of the iron impurity atoms, which results in the violet or purple colour of amethyst. Heating most amethyst to about 450°C causes it to bleach to colourless or pale yellow. Continued heating causes precipitation of iron oxide particles, which causes a deeper yellow. Most citrine on the gemstone market is such heat-treated amethyst. Because the colour is caused by uniformly dispersed iron oxide particles, this citrine is not pleochroic, that is, it does not show different intensities of colour when viewed in different crystallographic directions. Heat treated amethyst usually shows evidence of Brazil law twinning, often with colour zoning.
Some amethyst, when heated, turns green. Natural prasiolite is very rare and probably results from natural heating of amethyst. Most prasiolite on the gemstone market is artificially heated amethyst. This colour is produced by another change in the bonding of the impurity iron atoms, rather than by the precipitation of iron oxides. This material comes from only a few sources, mainly the Montezuma mine in Minas Gerais, Brazil.
Prasiolite itself can be subjected to artificial gamma irradiation and subsequent heat treatment to produce so-called ‘blueberry quartz’. This is a deep violet blue and resembles tanzanite.
Heating amethyst above 500°C not only bleaches it but can produce a milkiness, resulting in so-called ‘neon quartz’. This looks like lilac-coloured rose quartz. Stronger heating bleaches out the lilac colour completely and tiny water droplets form in the quartz. This material resembles adularescent gem materials and may be used as imitation moonstone.
Natural ametrine is bicolour quartz, purple and yellow, mainly from the Anahí mine in Bolivia. The colouring process is complicated. It involves differing concentrations of water in different growth sectors of the crystal and natural irradiation acting on the water to inhibit the formation of the purple colour in those sectors. Artificial heat treatment of ametrine to bleach the amethyst sectors can produce bicoloured citrine/colourless stones, sometimes marketed as ‘Lunasol’.
So much for Fe-bearing quartz. What about Al-bearing quartz? Usually the concentrations of aluminium in quartz are much higher than iron. Low levels of natural irradiation of Al-bearing quartz produces natural coloured citrine – yellow, yellow-green to yellow-orange. The details of the production of colour with irradiation in Al-bearing quartz is not well understood, but with increased levels of gamma irradiation the colour darkens, producing smoky quartz, and eventually black morion. Obviously, these colours also can be produced artificially with gamma irradiation, as is the case with the black Arkansas quartz.
Al-bearing quartz can also contain lithium in significant quantities. If is it lithium-poor, morion can be bleached by heat treatment to produce smoky quartz (and presumably some yellowish smoky quartz could be bleached to citrine). If Al-bearing morion, either naturally or artificially produced, is also lithium-rich, then gentle heat treatment at below 280°C can produce yellowish-green ‘lemon quartz’.
The distinctive characteristics of untreated and treated Al-bearing quartz are that if it is coloured it is pleochroic, and that it does not show evidence of Brazil law twinning. So naturally coloured citrine will show pleochroism from pale to intense yellow and no Brazil law twinning, while citrine produced by heat treatment of Fe-bearing amethyst will show no pleochroism but Brazil law twinning may be present. Lemon quartz produced by heat treatment of Al-bearing smoky quartz will show yellow to yellow-green pleochroism but no Brazil law twinning.
Other quartz varieties exist too. ‘Greened amethyst’ is produced by artificial gamma irradiation of pale amethyst containing a very high content of water, from southern Brazil. The resulting crystals can be a deep green, with a ‘greasy’ lustre. This green quartz shows red under the Chelsea Colour Filter, while Fe-bearing prasiolite shows green. Heating above 500°C produces a cloudy opalescence due to exsolved water in very fine droplets.
Common pink rose quartz, generally described as ‘massive’ although it is crystalline, is thought to owe its pink colour to tiny included crystals of pink dumortierite. The cloudy appearance is due to scattering of light from these tiny inclusions. (In some material these inclusions must be crystallographically orientated, because they can produce asterism.) The much less common rosettes of pink quartz, usually on a white quartz crystal matrix, are essentially different from massive rose quartz. These clusters of pink single crystals have colour attributed to aluminium and phosphorus. Gamma irradiation can intensify the colour of these rosettes of single crystals to a stronger purplish pink.
28th Mar 2015 15:47 UTCOwen Melfyn Lewis
-------------------------------------------------------
> The Journal of Gemmology (2012 Volume 33 Nos. 1/4)
> had an article by Ulrich Henn and Rainer
> Schultz-Güttler called ‘Review of some current
> coloured quartz varieties’. For those who
> don’t have access to this journal, published by
> the Gemmological Association of Great Britain,
> here is a summary of the article that I wrote for
> our local gem and mineral club's newsletter, to
> help distinguish the different varieties. These
> descriptions of the different colour varieties of
> quartz are those of Henn and Schultz-Güttler, and
> should not be ascribed to me, although I hope this
> gemmological approach helps clarify the
> mineralogical discussion.
Well respected as those gentlemen are, they describe their paper as a 'review'. I.e. there is no claim to any original work or opinion but a simple reporting to the work and views of others. Fair enough. Such collection and condensation of information is a valid and valuable exercise in itself. However, its greatest value is in the bibliography of the primary (and other) sources used which should be appended. For the best understanding, one needs always to read what was written by the original researchers. Not infrequently, when one tries to do this one finds reviews sometimes simply reference earlier reviews. Where such is the case (and it seems to happen too often for comfort), the door is open to the propagation of the dubious and even the creation of myth.
I am sure that these gentlemen must have appended their (extensive?) bibliography to their review. I for one would much appreciate a sight of that. In the absence of the bibliography, I find the following puzzling in your precis of their review.
> We all know that quartz occurs naturally in
> various colours with varietal names – colourless
> rock crystal, yellow citrine, purple amethyst,
> pink rose quartz, brown smoky quartz, black
> morion, and the rare natural green prasiolite.
> Some of these colours can be produced artificially
> by radiation, sometimes coupled with heating.
This seems to miss the basic point that irradiation and thermal agitation (heating) frequently have opposing effects. Irradiation driving a colour change in one direction and heating in the reverse direction - up to the point where thermal agitation is sufficient to destroy the colour-changing mechanism breaking the cycle of reversibility. This is true not only in quartz but across a range of transparent minerals capable of showing color (e.g. beryl and spodumene).
> Artificial heating can also lighten some dark
> coloured quartz.
*All* heating (thermal agitation) does this. The governing adjective 'Artificial' has no place here as it can only mislead. The cause of the heating is immaterial to its effect.
> First let’s consider Fe-bearing quartz.
> Naturally occurring clear Fe-bearing quartz
> crystals can experience low-level gamma
> irradiation from radioactive minerals in the
> surrounding rock. Over long periods of geological
> time this produces a change in the bonding of the
> iron impurity atoms, which results in the violet
> or purple colour of amethyst.
Insufficient for purpose here. There are important differences in quartz colouration arising from whether the Fe is present in ferrous or ferric form. This needs at least to be outlined or else understanding of the significant differences arising therefrom is not possible.
> Heating most amethyst to about 450°C causes it to bleach to
> colourless or pale yellow.
Ferrous/ferric?
- Continued heating
> causes precipitation of iron oxide particles,
> which causes a deeper yellow.
This is a mis-description, I think. 'Precipitation' implies solid particles coming out of solution, which is strictly not the case. Citrine (see my previous post) only forms where there is some SI+++ substitution by Fe+++ present in the quartz lattice. The yellow citrine colour is caused by a ligand field effect (as it is also in heliodor). The darkening of citrine to orange by heating to 500-550 deg C results from changes in the bonding between Fe and O to change the molecular structure creating a different iron oxide. The important point here is that the change is at the molecular level, sparse and with the molecules being too small to affect the transmission of light (i.e. the often perfect clarity of the material). To chase a more complete and detailed explanation of these processes, see 'The Physics and Chemistry of Color' by Nassau K. (Esp. Chap 9 and pages 192-194 in particular. See also 'Gemstone Enhancement' by the same author, (a noted original researcher, physicist and crystallographer) pages, pages 153-159.
> Because the colour is caused by uniformly
> dispersed iron oxide particles, this citrine is
> not pleochroic, that is, it does not show
> different intensities of colour when viewed in
> different crystallographic directions.
Citrine is generally held to show a very weak dichroism, sometimes absent. Pleochroic effect is related to the optic axes of a coloured anisotropic crystal and not to the crystallographic axes. The difference may be subtle but is important. That this is so is easily proven by anyone observing dichroic changes through a calcite rhomb dichroscope and rotating the tube of the dichroscope whilst the position of the crystal axes relative to the viewer remains unchanged.
> Heat treated amethyst usually shows evidence of Brazil
> law twinning,....
Moderate heating quartz (either geothermally or anthropomorphically) neither creates nor destroys twinning, Brazil Law or otherwise. If the heating is strong enough to melt the crystal, that is a different ball game but not within the scope of this discussion.
> .... Usually the concentrations of
> aluminium in quartz are much higher than iron. Low
> levels of natural irradiation of Al-bearing quartz
> produces natural coloured citrine – yellow,
> yellow-green to yellow-orange.
This is mistaken I think. Irradiating quartz that has some Al in place of Si in the lattice produces smoky -> morion. Heating smoky carefully can give lemon quartz (see previous post). See the references already given where the writer draws on his own original and peer-reviewed researches as well as drawing on the original research reports of others.
>The details of the
> production of colour with irradiation in
> Al-bearing quartz is not well understood, but with
> increased levels of gamma irradiation the colour
> darkens, producing smoky quartz, and eventually
> black morion.
No. Irradiation produces smoky, as stated. There is no intermediate colouring stage. The process *is* well understood and documented in detail by the primary researchers.
Not sure whether these sharp differences are occasioned by the review that you precised here or whether they result from the precising process itself. What ever, you may wish to check some of the primary research reports for yourself. If the two seminal works referenced above are not already on your bookshelf, any public lending library will make them available to you given time - as may any friendly university librarian where there is a decent materials science faculty.
28th Mar 2015 16:48 UTCDuncan Miller
-------------------------------------------------------
> I am sure that these gentlemen must have appended
> their (extensive?) bibliography to their review. I
> for one would much appreciate a sight of that.
>
> Not sure whether these sharp differences are
> occasioned by the review that you precised here or
> whether they result from the precising process
> itself.
As you are in Britain, I suggest you ask a local library for a copy of the Journal of Gemmology article, which has 37 references, and then take issue with the original, and my summary if necessary.
28th Mar 2015 18:49 UTCOwen Melfyn Lewis
No need: there are no issues here other than as already stated, I think. Who said what to whom and about what is not my concern at all (though, possibly, one for you?). You will know that many concepts remained theoretical until they could be clearly demonstrated through crystal synthesisation. Whilst crystal synthesisation has some of its roots in the early 19th century, most of the advances in theory and practice have occurred in the last sixty years or so.
In the case of ametrine (the subject of this thread), it first became generally known as a synthetic crystal, this causing all manner of grief through early pedantic denial that the first ametrine brought to market as natural was, truly, just that and not synthetic. The essential truths in respect to Al and Fe trace-level impurities in quartz have all been thrashed out since WWII, the truths of ametrine being discovered only in the late 1980's and published (in English) in the 1990's. Precursor work on the synthesisation of amethyst was done mainly in the 1970s and synthetic amethyst was still a novelty to the gem market even in the early '80s. All seems but yesterday in the lives of some of us.
The writings of Nassau, a life-long research scientist of note are truly worth reading. Of all his books and many research papers, perhaps the work he will be most remembered for is his 'The Physics and Chemistry of Colour. The Fifteen Causes of Colour'. Published in 1991, it remains the standard work on the topic and a grad/post-grad level primer for those needing a 450-page blister of knowledge in that fairly narrow field; knowledge that is one fundamental across most science and many, widely disparate, industries.
28th Mar 2015 19:27 UTCElise Skalwold
Thank you so much - that is an excellent and very readable summary of the JoG article! Only someone with your background in teaching and geophysics could distill it with such accuracy and clarity! The original JoG article is pretty dense reading with its lengthy and highly technical overview of Dr. Henn and Dr. Schultz-Güttler's primary research on cause and alteration of color in quartz, as well as the research of others in the field. I was fortunate to attend Dr. Henn's fascinating presentation on this in London at a conference in 2008 (later I had a chance to obtain some of their "blueberry quartz" to study; along with natural and synthetic ametrine, one of my favorite subjects).
Best wishes,
Elise
Duncan Miller Wrote:
-------------------------------------------------------
> The Journal of Gemmology (2012 Volume 33 Nos. 1/4)
> had an article by Ulrich Henn and Rainer
> Schultz-Güttler called ‘Review of some current
> coloured quartz varieties’. For those who
> don’t have access to this journal, published by
> the Gemmological Association of Great Britain,
> here is a summary of the article that I wrote for
> our local gem and mineral club's newsletter, to
> help distinguish the different varieties. These
> descriptions of the different colour varieties of
> quartz are those of Henn and Schultz-Güttler, and
> should not be ascribed to me, although I hope this
> gemmological approach helps clarify the
> mineralogical discussion.
>
29th Mar 2015 17:17 UTCDuncan Miller
29th Mar 2015 18:48 UTCOwen Melfyn Lewis
One of the best things in studying Nassau's writings is that not only was he always clear and precise but - the mark of a truly great man - when he did not know something he was not in the least shy of saying so publicly and in the process of doing so encouraging a spirit of further enquiry in his readers. As an 18-year old, I once took a memorable lecture from Lawrence Bragg (then in the evening of his days). I remember him too as having that same quality of refreshing frankness and being able to light a fire in people. It's truly a great gift.
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