Friday, August 26, 2016

KÖTTIGITE (ARSENATE), UMLAUTS AND BEAUTY



Life is full of beauty. Notice it. Notice the bumble bee, the small child, and the smiling faces. Smell the rain, [see the small minerals]and feel the wind. Live your life to the fullest potential, and fight for your dreams. Ashley Smith

The arsenates are perhaps my favorite group of minerals, and along with the phosphates and vanadates, have received several postings in my Blog (i.e. copper arsenate: olivenite and clinoclase and cornwallite; and copper, zinc arsenate: austinite; cobalt arsenate: erythrite; lead arsenate: mimetite; nickel arsenate: annabergite).  In these three groups arsenic (As) or phosphorous (P) or vanadium (V) combine with oxygen (O) to from the arsenate (AsO4), phosphate (PO4) and vanadate (VO4) radicals.  Each of these radicals, with a negative charge of 3-  then combines with a positive charged cation metal(s) and often with water (H2O) or hydroxide (OH) to form a wide variety of minerals.  Since the three radicals are approximately the same size they often substitute for one another in a solid solution series.  For example, pyromorphite [lead phosphate [Pb5(PO4)3Cl] is in solid solution with mimetite [lead arsenate Pb5(AsO4)3Cl].  The latter mineral is usually a pale yellow to yellow-brown color while pyromorphite is usually green to yellow-green in color; however, intermediate stages in the solid solution series are known (from work with XRD or EDS or other gizmos).  Each of these radical groups may also combine with a variety of metals that often form solid solution series with each other.  For example, erythrite [cobalt arsenate] is in a complete solid solution series with annabergite [nickel arsenate] as the cobalt cation substitutes for the nickel cation: Co3(AsO4)2-8(H20) to Ni3(AsO4)2-8(H20). Therefore, it is easy to understand the wide range, number and variety of arsenate, phosphate and vanadate minerals when so many combinations of cations and radicals are possible.

Many arsenate—phosphate—vanadate minerals are bright in color, have easily observable crystals and are widely available at mineral shows.  Therefore, I am a sucker, actually a buyer, whenever these minerals are located at shows (if the price is right)!

The 13 July 2015 Blog Posting described pink erythrite (cobalt arsenate) and green annabergite (nickel arsenate) and noted that a zinc arsenate mineral called köttigite is the zinc analogue [Zn3(AsO4)2-H2O] of both minerals. Therefore, I have been on the lookout for this fairly rare mineral and was delighted when I was able to pick up three small specimens at $1 each (a great price) collected from the Mina Ojuela, Mapimí, Durango, México.  Moore and Megaw (2003) described the Ojuela Mine as Mexico’s greatest mineral locality with 117 species known from the deposit including the world's finest adamite (in a gorgeous array of colors and habits), legrandite, kottigite/parasymplesite, and paradamite, as well as superb specimens of scorodite, hemimorphite, plattnerite, aurichalcite, rosasite, fluorite, calcite, wulfenite and other species. Mina Ojuela is also the type locality for paradamite, lotharmeyerite, metakottigite, mapimite and ojuelaite, and the co-type locality for scrutinvite.  The area was first mined by Spanish invaders in 1598 and was commercially mined for 350 years.  Today a few specimen miners still haunt the drifts and adits.

Bob Jones, one of my heroes in the world of minerals, noted in his 2011 book entitled The Frugal Collector that “of all the species from the Ojuela mine, perhaps the least eye-appealing is köttigite, which is a relatively dull blue-gray mineral.”  Hero or not, I do not agree with Bob’s opinion! I consider my three specimens as quite appealing and beautiful with very nice sprays of prismatic crystals.
 
Spray of köttigite crystals showing a distinct color variation from bottom (blue-gray) to top (clear).  This variation may be due to the amount of iron replacing zinc.  The S is water-clear selenite gypsum.  The ? are probably larger crystals of  köttigite while the “yellow” mass is unknown. Photomicrograph width FOV ~1.5 cm.

The dark blue-gray center spray of köttigite is very iron rich while a smaller spray to the left has rather clear crystals.  The S is selenite gypsum while the G is goethite.  Photomicrograph width FOV is ~1.5 cm.

Mixed color spray of köttigite and water-clear selenite gypsum (S) and goethite (G).  Width FOV ~1 cm.  

Köttigite, according to MinDat, should have colorless crystals but due substituting chromophores it shows a variety of colors ranging from red to red-orange to brown to rose pink to gray to gray blue (and probably more).  The prismatic crystals have a silky to waxy luster, are soft (2.5-3.0), are flexible and are transparent to translucent.  The mineral may also appear as encrusting rather than forming nice prismatic crystals.

Köttigite is formed in the oxidized zone of polymineral ore deposits by the alteration of primary hypogene minerals skutterudite [CoAs2] and sphalerite [ZnS]. Köttigite is the zinc analogue of, and in solid solution with, erythrite (cobalt arsenate) and parasymplesite (iron arsenate).  In fact, as köttigite obtains more and more iron the crystals become gray to light green to blue to greenish black and as I understand the situation, it is almost impossible to visually distinguish between köttigite and parasymplesite in many/most specimens.  Therefore, some technical journals use a hyphenated mineral name unless a chemical analysis has been completed. In addition, köttigite (Monoclinic Crystal System) is a dimorph (same chemical formula but different crystal system) with metaköttigite (Triclinic Crystal System).

I have learned much from this little project, especially about how the swapping of metallic cations and substitutions of the radicals can produce an amazing number of minerals.  But most importantly, I learned how to produce, in WORD, a diacritical mark called an umlaut.  You have all seen an umlaut, those two little dots over a vowel as in köttigite indicating “a partial assimilation to a succeeding sound. Used primarily in German.” If you really want to pronounce köttigite correctly go to www.webmineral.com and type in the name and look for the voice button.

I tried to learn German one time about a decade ago—spent six weeks taking a class in Germany.  This exercise was a tough assignment and about the only actions learned were phrases to order dark beer, sausage and pig knuckles, and bread.  On the final day of class our instructor took us to a nice outdoor café for lunch and we needed to converse with the staff—in German.  OK, I ordered food and beer but what about more conversation?  So with my very limited vocabulary I asked the wait staff if she would like to go dancing on the beach in the moonlight!  That was about the only sentence I could muster except one telling her about my dog and his name.  I think my instructor was humiliated; however, I did receive an extra desert from the staff!

REFERENCES CITED

Moore, T.P. and P.K.M. Megaw, 2003, Famous mineral localities: The Ojuela Mine, Mapimí, Durango, Mexico: Mineralogical Record, v. 34, September.

As for the beauty of köttigite I like the words of Tadao Ando: you can't really say what is beautiful about a place [mineral], but the image of the place [mineral] will remain vividly with you.




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