Re: absolutes, CO2 extracts

[Guest guest]

--- jimmyfresno123 <jimmyfresno@...> wrote:

I think that most of the basis for pushing

> CO2 extracts is

> that there is more extractable material available

> from essentially

> rare materials like agarwood and sandalwood to sell

> with the illusion

> that it somehow approximates finely distilled

> aspects of the same

> aromatics.

>

I am not very knowledgable on this subject but it

seems to me that C02s are not replacements for

distilled oils but rather complements to the oils.

They give the natural perfumer a chance to expand the

palette because they bring out different aspects of

the materials and, in some cases, they allow us to use

materials that are not easy to extract in other ways.

Some of them also allow us to bring an aromatic to the

heart of a perfume which would tend to stay on the top

if one were to use only the essential oil. Some of

the spices, for instance, are far more tenacious in

the C02s. Again, these are only my impressions and I

am no expert.

__________________________________________________

[Guest guest]

At 02:57 AM 10/12/2006, you wrote:

>I am new to the group and read some of the educational material on

>absolutes vs. essential oils, vs. CO2 extracts: how they're defined,

>resulting compounds, etc.

>

>I don't know if anyone else feels this way, but it mildly irks me to

>see some retailers describe CO2 extracts as somehow " truer " to the

>raw resource, or more cost-effective, or further to state that " there

>will not always be a basis for price comparison. " It seems to me like

>a long-necked stretch to blur the basis of comparison, to lead me to

>believe that absolutes and C02 extracts have some ethereal qualities

>that are unattainable otherwise. Yes, they do. But they run counter

>to the art of fine distillation in the same sense as a pile of orange

>rinds is truer to orange than essential oil of orange zest. I can't

>use plant sterols and wax in my cologne, and I dont' want to pay

>essential oil prices for components that have to be filtered out of

>the end product as heavy sediment: lignin, sterol, waxes, or anything

>that will mate with a carbon dioxide molecule donor during the

>process..I think that most of the basis for pushing CO2 extracts is

>that there is more extractable material available from essentially

>rare materials like agarwood and sandalwood to sell with the illusion

>that it somehow approximates finely distilled aspects of the same

>aromatics.

Hi Jimmy:

Whew! You sure are the investigative, analytical type, and I admire

that. I'm rather airy and let-it-go type, and I think the best is a

balance in between, lol.

I don't mind filtering, any more than I'd mind filtering coffee

grounds or tea leaves. Heck, I tincture all kinds of stuff, meaning

living flowers and leaves from my garden, seaweed, mushrooms,

sugar(!), bee goo, etc., so I have a lot of expensive alcohol that

gets lost in the process, too. Write it up to the cost of doing

business. Perfumery IS expensive, fact of life.

About CO2s, of which I am NOT an expert: I think they were originally

developed for the flavoring industry. Now, the natural perfumers have

made a run for them. Total v. select and all that. Very intereseting

to see the differences when the extractor-person goes for a certain

quality of scent, stopping the process at a certain point.

>In my thinking, yes, they offer nice, muted, whole

>olfactory " references " to a complete plant materials, but much of

>that nuance is lost in compounding an actual alcohol-based perfume,

>which relies on the very volatility that is absent in CO2 extraction.

I never put it so, but I think you have summed up why I don't use

them in my perfumes.

>To form a more apples-to-apples comparison of usefulness, the less

>volatile components should be fractioned off before the perfuming

>public is coaxed into buying these compounds as roughly efficacy-

>equivalent to hydrodistilled essential oils. True, essential oils are

>invariably denatured to some degree or another by the heat required

>to distill them, but this is an extreme form of the heat energy that

>also will release them on the skin for us to smell. I am sure I have

>oversimplified this debate, but to no less extent than marketers of

>CO2 extracts extoll their many benefits, true? I would love to hear

>some others' ideas about this subject which has always bugged me.

I have no idea what the above paragraph truly says, being the

non-scientific type! LOL.

I can add one bit about the hydrodistilled EOs, as they're called. My

understanding is that the concretes are distilled, giving us the HDEOs.

Well, I did an odor intensity and odor longevity test on several of

them a few months ago and I found them not to be any better than the

concretes or absolutes in either intensity, longevity OR quality of

scent. It's in the archives somewhere. Since they're 4 to 6 times the

cost of the concrete, I voted a big pass on them. Still wondering

what market they're aimed at.

Anya McCoy

Anya's Garden of Natural Perfume http://anyasgarden.com

Artisan Natural Perfumers Guild http://artisannaturalperfumers.org

Natural Perfumers Chat Group

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[Guest guest]

I can see your point, . I'm certainly no expert either. I have

used them in heart notes too, as a warming, full note. Agarwood's and

oak moss' musty " forest floor " notes are very interesting. I do have a

hard time with the ubiquitous " maple syrup/brown sugar " quality many of

them share, which I don't always particularly want. Someone else would

probably know why this is, but I am wondering if C02 extraction

concentrates sugars and oxidizes them like caramelizing sugar.

Overanalytical? Me?

My CO2 tyrade represents a couple of years of not being able to voice

this opinion about C02 extracts with anyone who would understand it. My

problem with them is the overzealous spin that a few distributors use

in describing them. Anyway, i got overly descriptive about a simple

concept: they contain a lot of insoluble, un-aromatic detritus There! I

feel like a new man.

>

>

> __________________________________________________

>

[Guest guest]

>

> I can see your point, . I'm certainly no expert either. I have

> used them in heart notes too, as a warming, full note. Agarwood's and

> oak moss' musty " forest floor " notes are very interesting. I do have a

> hard time with the ubiquitous " maple syrup/brown sugar " quality many of

> them share, which I don't always particularly want. Someone else would

> probably know why this is, but I am wondering if C02 extraction

> concentrates sugars and oxidizes them like caramelizing sugar.

> Overanalytical? Me? \

Hi - I have 2 cents to offer on this one.

I do not think the CO2s are in any way substitutes for the distillates.

Vetivert CO2

illustrates this better than any other material in my opinion.

Mu love of these oils is, as someone stated, the way in which they extend the

palate

available for experiencing the aromas of substances I am so fond of in their

natural forms,

but which become distorted and somewhat damaged during the distillation process.

I think there is a good deal of " we like what we are used to " in all of this.

If we become

acclimated to distilled oils, we come to see them as the standard. When we

compare an

extract (by whatever method) it seems different, and we are tempted to see it as

" bad " .

But this could be habituation as much as some true instrinsic superiority.

Some things are clear cut: the hassle of dealing with non-soluble components.

In this

respect, I think we just need to look at the CO2 oils (totals especially) as

essentially a

concrete. After all, a concrete is an extract not using alcohol, thus

containing non-alcohol

soluble components, by definition requiring further processing - you just go use

them

with this as your starting assumption. As we all know, a concrete is rendered

into an

absolute by extraction with alcohol and subsequent filtration and evaporation

of the

same.

Since CO2 oils are often (should be, anyway, once the technology investment

costs are

offset by longer-term business) less expensive than distilled equivalents,

perhaps they

literally should be categorized in the same class as " concretes " - that is,

extracts that have

not been rendered 100% alcohol soluble and thus need further processing.

Perhaps we

will someday see " hexane concretes " and " CO2 concretes " for sale - this seems to

be more

true to the nature of the products.

But, the practical issues asside, there are some aromas that you just can't get

with a

boiled, cooked, essential oil. There is nothing delicate, ethereal, mystical or

subtle about

distillation: you are cooking the heck out of the plant material, and trying to

not damage

the aroma too much in the process. The idea of low-temperature extraction like

the

florasols or CO2 oils that do not require heating has obvious advantages when

(regardless

of sediment) the goal is to capture the subtle nuances of aroma. There has to

be less

chemical change because as you learn in Chem 101, increasing the temperature of

a

system increases the rates of chemical reactions (in this case, alterations of

the aromatic

materials in the plant we hope to mimic).

Example: there is an aspect of sandalWOOD aroma (not sandalwood OIL aroma,

which is a

cooked, processed material) that you just can't get with distilled sandalwood.

I personally

am more acclimated to the aroma of real sandalwood chips, and to me the

(admittedly

wonderful) sandalwood distillates just don't capture the fine aroma of great

quality Mysore

chips heated gently over a mica plate. Not even remotely close - the distillate

is a mere

ghost of the actual raw material. My discovery of some decent sandalwood CO2

oils

(which I am now hoarding all remnants of) has enabled me to create sandalwood

blends

that release this subtle aroma in spades. Getting the blend right is hard - the

CO2s totally

over-emphasize the maple/carmel notes - like absolutes they are way too

concentrated

and need to be diluted down to 5% or beyond to begin to resemble the material

they are

intended to reproduce.

So, I guess it all boils down to intent and convenience: you would avoid a CO2

for the

same reason you would avoid a concrete - processing is required. If you are

tuned into

the distilled oils, and conceive of perfumes as blends of just these materials,

the CO2s will

never be a substitute.

If you are working to create a sublime rendition of a natural material, however,

like

sandalwood, you won't get close with the distilled oils (my opinion). You need

to work

with strong tinctures or good CO2 extracts. For my personal sandalwood

perfumes, I add

a CO2 total to a distilled oil so it is just above the perceptive threshold.

The CO2 has

better tenacity (lower volatility) so its presence grows over time. The result

is a

sandalwood aroma that makes me feel like I have my nose buried in a pile of the

finest

wood chips - a goal that had eluded me for many years.

Ok - that's enough, I imagine! I have really come to appreciate many of the CO2

oils, so

figured I should chime in.

[Guest guest]

Hi, Betasantalene.

I took notes from your post, thanks for all of the good information

on CO2 extracts. Maybe I have just been using higher concentrations

than necessary?

I got lots of ideas from your post for more rounded accords. I'm

going to try toning down some of my compositions. With perfumery

being such a subjective field, I am sure that 9/10ths of this is

basically based on what'cha think smells good.

This is an arcane thread, but worth discussing if the premise is that

we're mimicking the original plant material, which isn't always the

case. Being new to this, I'm fascinated by the theory and science of

perfumery, and not just the nice resulting smells, which I love as

well.

Some would argue that this thread dissects the subject way too far,

so I hope others are interested in this too. Understood that C02 vs.

EO is not an either or argument and there is a continuum of

usefulness for both. My question is whether CO2 extracts really offer

a truer reference to the full gestalt of the full botanical. My

(underinformed, academic) argument is that the overwhelming caramel

note to many C02 extracts isn't an inherent component of the

botanical, so much as it is evidence of degradation as part of the

cost of the C02 extraction process.

Back to your Chem 101, doesn't the carbon atom donated by the C02

actually " caramelize " the saccharide chains (sugars) in the same way

that sugar is caramelized? (And in the spirit of full disclosure,the

C02 IS heated to an extent, right?) What's left in the exudate

(pressurized!) is now subjected to oxidation by the the leftover 02

molecules with a host of wonderful substrates to now oxidize, unless

there's a hydrogen molecule around to form... water! The result?

Basically the maple syrup we then need to dilute in order not to

detect. Theoretically, an impurity to my nose. Perhaps the less woody

botanicals are the ones with less cellulose (complex carbohydrates)

to turn into brown sugar?(Also, I was curious about your name. Is

betasantalene the same as beta santalol, the second volatile isomer

in sandalwood oil?) Will eagerly await more information.

[Guest guest]

Hi Anya. Thanks for the information on this. I do over-analyze this

stuff, which is probably why I was attracted to perfumery. It's a ripe

subject matter for dissecting. I actually love the scientific aspects

of perfumery and hadn't had access to people who knew so much about it!

I guess I'm a direct contrast to some of the people who approach

perfumery in an imagery-guided or spiritual way. I'll bet we all

approach it from different angles and complementary, which I'll bet is

why you formed this great group, LOL!

[Guest guest]

> (underinformed, academic) argument

Well, we have something in common, it seems!

>is that the overwhelming caramel

> note to many C02 extracts isn't an inherent component of the

> botanical, so much as it is evidence of degradation as part of the

> cost of the C02 extraction process.

>

My (long) message was a lot of opinion, so I hope the notes are actually worth

something.

I have read only brief summaries of the CO2 process and don't have any

expertise.

To my nose some of the CO2 oils capture certain aromatic notes not captured by

other

methods, which is NOT the same thing as saying they capture all of the aspects

of the

smell in the same proportion as is found in the raw material itself. Every

solvent will

concentrate certain materials over others, just like distillation concentrates

more volatile,

less water soluble materials. And no doubt degration and chemical change are a

given in

any process (though I though the whole point of CO2 as a solvent was that it was

non-

reactive, non-odorous, and easily separated).

Anyway, in my blending, some CO2 oils I have used have been most valuable in

terms of

the extreme tail end of their evaporation. To me, a good sandalwood CO2 is

absolutely

sublime in this respect - nothing else even comes close.

> Back to your Chem 101, doesn't the carbon atom donated by the C02

> actually " caramelize " the saccharide chains (sugars) in the same way

> that sugar is caramelized? (And in the spirit of full disclosure,the

> C02 IS heated to an extent, right?) What's left in the exudate

> (pressurized!) is now subjected to oxidation by the the leftover 02

> molecules with a host of wonderful substrates to now oxidize, unless

> there's a hydrogen molecule around to form... water! The result?

Ok: I just don't know much about CO2 extraction chemistry, it seems. I'm all

in favor of

academic discussions, for what it's worth, so here goes!

First, I am not sure about how much the CO2 is heated. Is it heated to

temperatures

approaching boiling water? The heat degradation issue would have to be about

both the

typical temperature and the exposure time. Anyone know how the heat exposure in

CO2

extraction compares to that in distillation?

Second, the question of carbon donation, carmelization, free oxygen production,

followed

by oxidation, is not something I know anything about. Is this something you

have read

about, is it common knowledge, or a hypothesis on your part? Does CO2 really

decompose to oxygen and pure carbon during the process of extraction to an

appreciable

degree?

My limited understanding of carmelization is that it is the result of high

temperatures and

is some kind of polymerization of sugars (I though temperatures way beyond the

boiling

point of water). When I learned about sugar polymerization in biology class, it

was in

terms of dehydration synthesis (basically, producing water as a byproduct), but

did not

involve carbon dioxide in any way. But that was just a biology class, after

all, and the

world of organic chemistry can take a lifetime to master, I imagine.

All a mystery to me, right now. I am going to see what I can find out about the

CO2

extraction process!

[Guest guest]

> First, I am not sure about how much the CO2 is heated. Is it heated to

temperatures

> approaching boiling water? The heat degradation issue would have to be about

both the

> typical temperature and the exposure time. Anyone know how the heat exposure

in CO2

> extraction compares to that in distillation?

>

Ok- I looked around on the web a bit. CO2 has a critical temperature of around

32 degrees

centigrade, so it does not have to be heated. I saw temperatures for

supercritical extraction

a bit warmer than this, around 35 - 50 degrees centigrade - basically at or

slightly above

human body temperature, so heating is not comparable to distillation (either

hydro- or high

pressure steam).

[Guest guest]

Edited to correct top post and *well* snipped. !!

From:

[mailto: ] On Behalf Of betasantalene

Sent: Friday, October 13, 2006 5:32 PM

Subject: Re: absolutes, CO2 extracts

<Big snip>

My limited understanding of carmelization is that it is the result of high

temperatures and

is some kind of polymerization of sugars (I though temperatures way beyond

the boiling

point of water). When I learned about sugar polymerization in biology class,

it was in

terms of dehydration synthesis (basically, producing water as a byproduct),

but did not

involve carbon dioxide in any way. But that was just a biology class, after

all, and the

world of organic chemistry can take a lifetime to master, I imagine.

All a mystery to me, right now. I am going to see what I can find out about

the CO2

extraction process!

The caramelization thing as it relates to the C02 process is more of a

hypothesis, although the chemistry behind caramelization of polyscaccharide

chains in general is very well-understood. It usually happens with low pH (a

factor left out of our discussion) or extreme heat. I can't help but

hypothesize that this caramel-y characteristic that seems present in so many

C02 extracts is not a mere coincidence.. sandalwood, agarwood, and I'm

guessing it is a direct result of caramelization of the cellulose.

[Guest guest]

At 11:33 PM 10/13/2006, you wrote:

>

>

> > First, I am not sure about how much the CO2 is heated. Is it

> heated to temperatures

> > approaching boiling water? The heat degradation issue would have

> to be about both the

> > typical temperature and the exposure time. Anyone know how the

> heat exposure in CO2

> > extraction compares to that in distillation?

> >

>

>Ok- I looked around on the web a bit. CO2 has a critical

>temperature of around 32 degrees

>centigrade, so it does not have to be heated. I saw temperatures

>for supercritical extraction

>a bit warmer than this, around 35 - 50 degrees centigrade -

>basically at or slightly above

>human body temperature, so heating is not comparable to distillation

>(either hydro- or high

>pressure steam).

That is what I remember, Beta. I think Butch is MIA right now, but

maybe he can comment. I think, I'm not sure-- that he knows about CO2s.

? Anyone else?

Hey, Will! WTH are you? LOL.

--

Anya McCoy

Anya's Garden of Natural Perfume http://anyasgarden.com

Artisan Natural Perfumers Guild http://artisannaturalperfumers.org

Natural Perfumers Chat Group

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[Guest guest]

>

> The caramelization thing as it relates to the C02 process is more of a

> hypothesis, although the chemistry behind caramelization of polyscaccharide

> chains in general is very well-understood. It usually happens with low pH (a

> factor left out of our discussion) or extreme heat. I can't help but

> hypothesize that this caramel-y characteristic that seems present in so many

> C02 extracts is not a mere coincidence.. sandalwood, agarwood, and I'm

> guessing it is a direct result of caramelization of the cellulose.

>

Ok - so was the original question is whether people should claim that CO2 oils

are

somehow " verbatim copies " of the aromatic spectrum in the raw material itself,?

That would be an unequivocal " no " for any extracted product or distilled product

since all

such methods favor certain substances over others (which are most

hexane-soluble?

Which have the lowest molecular weight? Which are most unstable when heated?

Which

are most alcohol-soluble? Which are most CO2 soluble?) Etc..

I would also add that I personally think that any attempt to classify a

particular extraction

method as " better " or " worse " will not go anywhere - the answer will inevitably

be " it

depends " . Absolutes are best for some materials, concretes better for

particular uses,

distillates may be more familiar or more refined in a particular way, tinctures

more subtle,

etc.., etc..

I think if the question is " which method is most likely to alter the structure

of individual

molecules in a plant " , then I believe distillation (esp. high pressure steam) is

likely to be

the most destructive. It's a matter of common knowledge that heat facilitates

chemical

change. I do know for a fact that the duration of heating is an issue - for

example, in a

low-temp. distilled sandalwood, certain oxidized materials are produced that are

not as

abundant in shorter-duration, high pressure distillations (these oxidized

products may

actually improve the aroma, in this case).

Anyway, if the merchant(s) you refer to said something like " the CO2 process is

least

likely to alter the structure of the molecules being extracted " , they might have

been telling

you the truth!

I am under the impression that extraction at body temperature with CO2 is least

likely to

cause chemical change - oxygen is excluded from the system (oxygen is the

ultimate

molecular re-arranger), there is not much heat involved, the extraction is

rapid, and the

solvent is a very non-reactive, inert molecule.

FYI, the issue of pH only applies to aqueous (water-based) solutions, since pH

is a

measure of the ratio of two byproducts of dissociation of water. CO2 extraction

of a dried

plant material is, by definition, not a situation in which the concept of pH

applies. CO2

does make a very weak acid (carbonic acid) when it dissolves in water. So CO2

extraction

of fresh plant material could be a situation in which pH is decreased a bit!

I have only seen the strong carmel note in sandalwood CO2 extractions, most

particularly

one batch of a " total " extraction (which is carried out under different

environmental

conditions than a select extraction). What materials have you seen in most

with? As far as

the total extracts go, here's where my understanding gets shaky... I believe

that CO2

selects are performedd at pressures and temperatures closer to the critical

point of CO2,

while total are extracted under more extreme conditions - increased pressure and

perhaps

temperature.

One article on CO2 extraction (no source, sorry) indicated that higher pressure

extraction

might hypothetically break molecules down a bit (the opposite of carmelization,

which is a

polymerization process that joins molecules). Perhaps, though, these broken

molecules

would change the aroma in some recognizeable way, or even re-join in odd

configurations

when the pressure was released? I don't know!

[Guest guest]

Beta, When Anya does " Natural Perfumery, The Movie, " hopefully your

part will be cast by Robin as his classic quirky professor of

an Ivy League chemisty class. Very good delivery of material, not to

poke fun of the nutty professor image that has now stuck in my mind.

As you say, I'm not sure we're going to find out whether carmelization

happens because of the CO2 extraction process or not. I do see several

articles in the flavor industry that speak about CO2 distillation of

meat products giving a " browning effect " to the distillate, being

useful for caramalized essences to be used in flavoring. Whatever the

case, we have probably dissected this more than is due for this general

discussion group and gotten to the point that basically says, 'use C02

exctracts if you like what they have to offer.'

You never did answer, though, so is it beta-santalene or -santalol?

[Guest guest]

> You never did answer, though, so is it beta-santalene or -santalol?

>

Ok -

This is kind of serendipitous, given this thread: it turns out that

beta-santalene is a

compound that I saw present at relatively high concentration in a GCMS report on

(surprise,

surprise) a CO2 extract of Indian sandalwood that I was particularly fond of.

So, beta-santalene is indeed beta-santalene. Beta-santalol is an alcohol,

beta-santalene is

an alkene (obscure molecular difference I only vaguely understand).

I was trying to come up with a unique handle and had the GCMS in front of

me at the

time...