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A new mineral: alpha-calcium formate
  
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Cesar M. Salvan
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PostPosted: May 01, 2021 15:56    Post subject: A new mineral: alpha-calcium formate  

Recently, we published the complete description of a new mineral found in the sediments of the Alkali lake (Oregon, USA).

The extraordinary crystals of what in a first view were identified as formicaite (beta-calcium formate) turned out to be the orthorhombic polymorph, alpha-calcium formate.
To me, this is a very interesting finding not only because it is a previously undescribed mineral, but because it is a very remarkable example of a biomineral formed in very peculiar conditions.
The accumulation of formate to the point of precipitation and crystallization of centimetre-size crystals implies that the biological consortium are not metabolizing formate, accumulated by the anaerobic fermentation of organic matter. We hypothesized that this situation could be explained by the unique ecology of the Alkali lake (extremophilic, highly saline and high pH) and/or by a dramatic chemical contamination episode that suffered the lake decades ago, when tons of organochlorine compounds derived from the industrial synthesis of "orange agent" polluted the Alkali lake system. In any case, it is extraordinary the size and quality of the specimens. We performed a simulation of the conditions of the lake, and to form those crystals in that size it is necessary a high local formate concentration. Whether completely anthropogenic or not, the specimens are remarkable and, if you have one in your collection, you have a piece of a unique biochemical process and a piece to think about the long term effects of our interaction with environment.

We explained all in our paper here:
doi.org/10.3390/min11050448

The work, lead by the group of Nikita Chukanov (who also described the formicaite), in opinion of one of the reviewers:
"This is a beautiful and sobering story of a new, probably anthropogenic mineral. I thank the authors for producing one of the most fascinating mineral descriptions I’ve read in a long time.", so, I am definitely proud to share it here. I should thank also to my friend Jordi Fabre, who kindly provided part of the samples we used in the study.

We are now looking for more occurrences of the "alpha-formicaite", in order to elucidate if it is an endemism of the Alkali lake or it could be formed in other conditions and entirely by natural processes. If you have or find possible calcium formate samples, please contact me.



caformate alkali lake (web).jpg
 Mineral: "alpha-formicaite"
 Dimensions: 2 cm
 Description:
The hair (an animal hair) in the crystals were trapped during crystallization.
 Viewed:  768 Time(s)

caformate alkali lake (web).jpg



caformate alkali lake3 (web).jpg
 Mineral: "alpha-formicaite"
 Dimensions: 2 cm
 Description:
 Viewed:  764 Time(s)

caformate alkali lake3 (web).jpg


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Volkmar Stingl




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PostPosted: May 01, 2021 23:27    Post subject: Re: A new mineral: alpha-calcium formate  

"...when tons of organochlorine compounds derived from the industrial synthesis of "orange agent" polluted the Alkali lake system...."

"...of a new, probably anthropogenic mineral..."

Then it should not be called a "mineral". Or am I wrong?
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SteveB




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PostPosted: May 02, 2021 02:09    Post subject: Re: A new mineral: alpha-calcium formate  

I am unsure and uncomfortable about it being called a Mineral. It may be a grey area. Its could be called a chemical compound, but so could what we call minerals, It could be called a Formate or a Salt. I’ve forgotten my Chemistry and we (people) redefine and reuse words to simplify things to suit ourselves. Often due to poor education involving over simplification and general dumbing down. It may be us using the word Mineral is incorrect?

But as the author points out its a single unique manmade situation where these crystals were then naturally formed. No doubt if someone looks close enough in other industrially polluted locations and systems other compounds will be found that would not be there from the natural geology.

Still this is a forum on rocks and minerals, The post is more in the chemical context of a mineral, maybe not entirely relevant here. Author seems to be wanting help to see if natural occurances are known and I suggest they research further on mindat where chemical makeups and crystalline structures recorded. It may be something already noted and named somewhere.

If they expect us hobbyists to find natural occurring specimens then a guide as to how would be useful as the equipment and techniques they used in the paper are far beyond most of us.

I’d like to know if these crystals are stable over time in air, or will they react over time to natural changes in humidity much like copper sulfate crystals can develop an opaque crust over time when exposed to air. If us collectors are not to waste time thinking barite and selenite crystals are the “new” compounds and to avoid ebay scammers growing platelet crystals of say sodium theosulfate as “newly discovered ultra raaarrree !!!!!!!! CrY$$tals” in order to profit from muddying everyones waters. Apart from showing us the Best examples what should we expect to find in the field if we are to find other occurances.
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Cesar M. Salvan
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PostPosted: May 02, 2021 05:17    Post subject: Re: A new mineral: alpha-calcium formate  

I think it is my post is relevant here, obviously. The admins are those that ultimately should decide if it is relevant here or not. If they decide it is not relevant, they should erase it and probably I should sorry for wasting my time sharing science here and stop posting.

The discussion about "mineral yes or not" is purely semantic here. Obviously the mineral is not a make-up or man-made. We did not demonstrate even that the calcium formate was formed as a consequence of one type of human intervention. It is just one of the possible hypotheses about its genesis. So, it is kind of ludicrous to discuss if it is a mineral or not because one of the hypothesis of its origin is a human intervention in the system. In my opinion, this alpha polymorph should be the commonest and it is probably completely natural. But we have no evidence to support any of the possible triggers that lead to the crystallization of the calcium formate.

The beta polymorph is a IMA accepted mineral (formicaite) and there are specimens of both, the alpha and beta polymorphs, in collections. I know that a number of specimens of the Alkali lake formate were put in the market. It is stable, not like the copper sulfate, and it is reasonable to think that someone could have bought one sample or found formates or formicaites that are actually the alpha polymorph. Probably they would appreciate all this information. Also, I know a lot of collectors and mineral hobbyist that are perfectly able to distinguish a baryte or selenite from something different, weird or suspicious of being a rare species. Precisely this is how we found a lot of new mineral species and completed the paragenesis of innumerable deposits. So, I am sure that a lot of collectors, in case of finding something like a crystal of calcium formate among the crystals of another alkaline lake, for example, would think "this is different from the usual gaylussite and so on".
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Roger Warin




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PostPosted: May 02, 2021 05:34    Post subject: Re: A new mineral: alpha-calcium formate  

Hello

Formicaite is located at the crossroads of two worlds of our planet: the mineral world and the organic world, resulting from living things, but also from stellar nucleosynthesis.
Formicaite is the salt that results from the action of limestone (CaCO3, or even Ca (HCO3) 2 in such wet conditions) and formic acid, so the molecule is very simple. It is the simplest of carbonic acids:
CH2O2, which has the structural formula H-COOH.

Formic acid
(structural formula)

Formicaite or Calcium Formate

The next compound is acetic acid (vinegar) CH3-COOH.
Formic acid is a natural product and it does not result from pollution.
It does not have chlorine. It is a weak acid.

As limestone is abundant, the formation of formicaite is therefore not uncommon. But it is relatively soluble in water (because acid carbonate).
What is truly exceptional is the rarity of automorphic crystals. This explains its late discovery. It was registered with the IMA in 1998.
Type locality:
Solongo B deposit, Vitim Plateau, Baunt District, Buriatia Republic (Buryatia), Zabaykalsky Krai, Russia.
Second locality: Alkali Lake, Lake Co., Oregon, USA.

Some remarks:
Formicaite is not of human origin.
To give a few examples of its natural presence on our soil, the venom and ants of bees contains it.
If nettles sting, it's because of formic acid.
Etc.
Carbon is one of the 92 natural elements.
In the case of your remark, the SiC molecule should be excluded from inorganic chemistry.
However, SiC moissanite was discovered by Moissan in the Meteor Crater.
We discover it in chondrites in the company of diamonds (also formally, an organic product!).
The moissanite accompanies the diamond in the kimberlite.
It is also one of the best imitations of cut gems, not very expensive and very hard.

But I agree that kidney stones are human. They are the result of good nutrition.
Roger.



Acide formique.jpg
 Mineral: Formic acid
 Description:
 Viewed:  626 Time(s)

Acide formique.jpg



Formicaite-bis.jpg
 Mineral: Formicaite
 Description:
 Viewed:  624 Time(s)

Formicaite-bis.jpg


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Pete Richards
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PostPosted: May 02, 2021 20:45    Post subject: Re: A new mineral: alpha-calcium formate  

The old notion that minerals must be free of anthropogenic or other biologic influence , and must be inorganic chemical compounds, has long become one of mostly historic interest, with some organic salts like whewellite long accepted as minerals, and with the realization of the frequency with which low temperature mineralogenesis is biologically, especially bacteriologically, mediated, as shown by isotope studies.

I have a sulfur crystal from Michigan. Studies of the isotopic composition of sulfur from this locality indicate that it was formed as a result of bacteriological decomposition of natural hydrocarbons. Is it a mineral? Is the sulfur from Sicily a mineral? How can I tell which is a mineral and which is not? How can I tell if MINE is a mineral or not, as opposed to the one that was studied?

Pyrite of low temperature origin also often shows the stamp of biological activity. It is a totally unworkable proposition that some pyrite is really pyrite and some is not, because of a biological influence. How will YOU find this out about YOUR specimens?

There certainly are grey areas, and always will be. But "minerals" intentionally made by humans to sell on the market, such as artificially produced silver wires, sulfur, and chalcanthite are and always will be fakes, not minerals.

The suggestion that Mr. Salvan " seems to be wanting help to see if natural occurances are known and I suggest they research further on mindat" is so far wrong as to be embarrassing, as the suggester might have found out if he had followed the link to the very thorough and well-reasoned article, to look more closely into this matter.

This forum presents ideas and information at many levels, and is moderated to avoid content the moderators deem inappropriate according to the forum's guidelines. It is not to be expected that every member will find every post useful to his or her own interests.

I thank Mr. Salvan for introducing me to a very interesting article about a unique mineral occurrence.

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James Catmur
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PostPosted: May 03, 2021 02:36    Post subject: Re: A new mineral: alpha-calcium formate  

Hear, hear. If we start trying to separate specimens (not minerals but individual specimens) into those that we think are ‘OK’ and those we think are the result of life, there lies madness.

Pete Richards wrote:
The old notion that minerals must be free of anthropogenic or other biologic influence , and must be inorganic chemical compounds, has long become one of mostly historic interest, with some organic salts like whewellite long accepted as minerals, and with the realization of the frequency with which low temperature mineralogenesis is biologically, especially bacteriologically, mediated, as shown by isotope studies.

I have a sulfur crystal from Michigan. Studies of the isotopic composition of sulfur from this locality indicate that it was formed as a result of bacteriological decomposition of natural hydrocarbons. Is it a mineral? Is the sulfur from Sicily a mineral? How can I tell which is a mineral and which is not? How can I tell if MINE is a mineral or not, as opposed to the one that was studied?

Pyrite of low temperature origin also often shows the stamp of biological activity. It is a totally unworkable proposition that some pyrite is really pyrite and some is not, because of a biological influence. How will YOU find this out about YOUR specimens?

There certainly are grey areas, and always will be. But "minerals" intentionally made by humans to sell on the market, such as artificially produced silver wires, sulfur, and chalcanthite are and always will be fakes, not minerals.

The suggestion that Mr. Salvan " seems to be wanting help to see if natural occurances are known and I suggest they research further on mindat" is so far wrong as to be embarrassing, as the suggester might have found out if he had followed the link to the very thorough and well-reasoned article, to look more closely into this matter.

This forum presents ideas and information at many levels, and is moderated to avoid content the moderators deem inappropriate according to the forum's guidelines. It is not to be expected that every member will find every post useful to his or her own interests.

I thank Mr. Salvan for introducing me to a very interesting article about a unique mineral occurrence.
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alfredo
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PostPosted: May 03, 2021 04:50    Post subject: Re: A new mineral: alpha-calcium formate  

Recently I showed a collector some whewellite crystals (calcium oxalate) I'd found inside a dead cactus in Tucson and he told me it wasn't a mineral because it was formed by biological processes, just like the whewellite crystals in a human kidney stone. But whewellite crystals in ore veins and clay-siderite concretions are indeed "minerals". To me this distinction makes no logical sense.

Ultimately, whether by biological or geological processes, or a combination of both, life was responsible for the majority of the close to 6,000 mineral species on Earth. And because there is LIFE on this planet we have such an incredible diversity of mineral species. The other planets in our solar system will all be relatively mineralogically boring. No photosynthesis means little free oxygen and no oxide zones. There won't be any beautiful specimens of vanadinite, adamite or torbernite on any other planet... thanks to life.
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Riccardo Modanesi




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PostPosted: May 03, 2021 12:40    Post subject: Re: A new mineral: alpha-calcium formate  

Hi to everybody!
There are plenty of minerals taking an organic or metallorganic origin: coronene, urea, whewellite, zanazziite are just some examples of them!
Greetings from Italy by Riccardo.

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Hi! I'm a collector of minerals since 1973 and a gemmologist. On Summer I always visit mines and quarries all over Europe looking for minerals! Ok, there is time to tell you much much more! Greetings from Italy by Riccardo.
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Cesar M. Salvan
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PostPosted: May 06, 2021 09:55    Post subject: Re: A new mineral: alpha-calcium formate  

A note on concepts for the gen pub here:

A same mineral could be biogenic or not. For example, sulfur, pyrite or even galena could be biogenic or the product of geochemical processes without direct intervention of life. There are a lot of minerals and mineral deposits of biogenic origin, both direct (produced by metabolism of bacterial consortiums, like the sulfide in the biogenic pyrite, and so on) or indirect (Earth oxygenation led to the formation of a huge number of oxidized minerals, for example).

There are also minerals that not only are biogenic, but are also only-biogenic, or more properly, biosignatures, i.e. its formation is directly linked to a certain biological activity and cannot be formed abiotically currently on Earth (note that I say currently and on Earth). For example, as cited, oxalates (like whewellite), struvite, simonellite, fichtelite, uricite, guanine... Simonelite and fichtelite, moreover, are useful biomarkers (products of diagenesis of conifer resin diterpenoids).

The calcium formate polymorphs, beta (formicaite) and alfa-calcium formate belong to these class of biominerals: on Earth are just biogenic.

On the other hand, we have the "official" use of the term "mineral". The biogenicity is not a demarcation criterion for a substance to whether should be included or not in the "official" list of accepted minerals. Also, the frontier between inorganic and organic is fuzzy and quite outdated. Obviously, an organic compound could be a mineral. And the duality between biology and geochemistry is also outdated: the biological activity is a geochemical agent, life and geochemical environment are intimately linked since origins of life, and there is no such distinction: Life creates minerals, and minerals aided in the life emergence.

But, when it comes to the anthropogenicity is when we put the feet in the frontier of the "official" terminology. IMA rules establish a clear cut in this case: when the "substance" is formed as a consequence of certain human interventions, like pollution of water or environment, it should not be considered a mineral. This is very practical: the human intervention will lead potentially to a huge number of weird chemicals.

What I think in this case? clearly our alpha-calcium formate is a mineral. To be an "official" IMA accepted mineral, we should rule out the hypothesis of its formation solely linked to water pollution. In my opinion, if another occurrence of calcium formate is found, it probably will be the alpha polymorph, as we think that the beta polymorph formicaite is formed in a more stringent and specific conditions. If we find other occurrences of calcium formate and clearly are not linked to the pollution of a lake, we will be able to list it in the IMA list of minerals.
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