Friday, October 19, 2018

ARSENATES AND OTHER MINERALS FROM THE OJUELA MINE


Mineralia 2011

An intransitive verb is an action verb, for example, suffer.  But if you stick an object with an action verb then the verb becomes transitive. A good example is Mike suffers (verb) pain (object) in the lumbar region of his lower back.

The dictionary tells me that pain is a basic bodily sensation induced by a noxious stimulus, received by naked nerve endings, characterized by physical discomfort.

Yep, I can agree about the pain. A condition called spinal stenosis is physical discomfort caused by narrowing of the lumbar spinal column that produces pressure on the nerve roots resulting in sciatica and a condition resembling intermittent claudication and that usually occurs in middle or old age. That is correct---it hurts to get old.

But, in today’s world there might be an opportunity to “fix” the stenosis and so it was I decided to undergo a bilateral lumbar laminectomy.  This procedure removed the back part (lamina) of the affected vertebra (L 2-4 in my case). A laminectomy is sometimes called decompression surgery because it eases the pressure on the nerves by creating more space around them.

And the leg pain sort of  disappeared.  In on Thursday out on Friday noon with nary a narcotic “pain killer” down my gullet after dismissal.  But there is the LBT—no lifting, bending, or twisting for several weeks.  Shucks, I can’t mow the lawn, shovel snow or lift a large bag of taters. However, a simple twist yesterday just about sent me through the roof.

But, the state of being weary and restless through lack of interest, also known as boredom, has struck.  It might not have stayed except a giant back brace (24/7 for 6 weeks) makes my desk chair rather uncomfortable.

So, time to bite the bullet.  Bite it really hard since I dug out a box of specimens from the Ojuela Mine (Mexico) tucked away marked "arsenates" but containing little other information.  I had picked these up from a dealer at Tucson a couple of years ago and had stuck them in the “To Do” box.  So out they came, and a couple were really tough to decipher for an ole soft rock person.

The Ojuela Mine in the Mapimi District, Durango, Mexico, is a polymetallic mine (mostly gold, lead, silver, zinc) with mineral formation in Mesozoic carbonates.  Although the mine produced a variety of metallic ores, it is best known for other reasons: 1) Santiago Minguin, the designer of the Golden Gate Bridge, executed the design and construction of a suspension bridge to the mine that is 1043 feet in length and anchored by two end towers; 2) beginning in the 1940s specimen mining started producing magnificent examples of adamite, paradamite, scorodite  and hemimorphite---some of the best in the world.  The mine has produced over 100 different minerals and is the type locality for six minerals.  It seems to be especially rich in arsenate minerals. 

So, on to my specimens. One was a piece (~4.5 x 8.0 cm) of limonite/goethite with several beautiful, butterscotch-colored, blocky crystals of the lead molybdate, wulfenite, perched on the surface.  This was an easy one to identify, although it was not an arsenate. Shucks.

Really nice blocky crystals of wulfenite on goethite/limonite.  FOV both ~3.3 cm. 


The next jewel in the box (~3.0 x 3.5 cm) indeed was a calcium copper arsenate, conichalcite (with nice “little green balls), CaCu(AsO4)(OH).
Green conichalcite spherulites; submillimeter in diameter.


Another two specimens (~1.7 x 1.0 cm and ~2.0 x 2.0 cm) took some sleuthing and I am not yet certain about the identification, but both are arsenates.  However, my guess is: 1) arsenbrackebuschite, a lead iron arsenate; and 2) the lead zinc arsenate, tsumcorite. Both are “microminerals.”

Arsenbrackebuschite is a real tongue twister.  According to MinDat.0rg the name originated with the lead manganese vanadate mineral, brackebuschite [Pb2Mn3+(VO4)2(OH)].  That mineral, in turn, was named for the German mineralogist Luis Brackebuschite.  In arsenbrackebuschite the arsenate ion replaces the VO4 [Pb2Fe3+(AsO4)2(OH)] and iron replaces the manganese.

Arsenbrackebuschite is a rather uncommon mineral found in the secondary (oxide) zone of arsenic-bearing, hydrothermal lead-iron deposits.  The co-type localities are at the Tsumeb Mine in Namibia and the Clara Mine in Germany.  The polymetallic mines at Mapimi have produced my specimens.  In contacting the dealer at a later date, I was informed that the tiny, poorly formed crystals had been identified by XRD and confirmed my visual identifications.  But the mineral is rare at the Ojuela Mine.

Arsenbrackebuschite is yellow to amber to red brown in color with some well-formed crystals having a shiny (sub-vitreous) to waxy luster while mine are more earthy, maybe resinous--and very tiny and indistinct.  Some better formed crystals have a hardness of ~4.5 (Mohs) although it would seem impossible to measure the earthy variety. It is a tough mineral to identify as even mineral photos on MinDat.org are measured in millimeters.
Photomicrograph of poorly formed, yellow-amber, submillimeter crystals of arsenbrackebuschite.  The total width FOV is ~6 mm.

If arsenbrackebuschite is tough to identify then a hydrated lead zinc arsenate, tsumcorite, is even more difficult.  Here the mineral has replaced the iron with zinc:  PbZn2(AsO4)2-2H2O.  Note that OH in arsenbrackebuschite is replaced by 2 water molecules in tsumcorite.  My chemistry is at an elementary level, but I believe that since the iron has a 3+ charge and zinc a 2+ charge then in order to balance charges it picks up an extra hydrogen.  I could really use some help from a reader more learned in chemistry!
I have identified these clove-brown, microscopic crystals as tsumcorite.  Width field of view ~11 mm.

Elongated, along C-Axis, double pyramids of submillimeter, light yellow wulfenite crystals.  

The type locality for tsumcorite is the Tsumeb Mine in Namibia and, in fact, the name comes from the mine owner—Tsumeb Corporation.  Again, this is one of those rare arsenates that is found in the oxide zone of arsenic-bearing, hydrothermal, polymetallic mines. It ranges from yellow-brown, clove brown, red-brown, or orange in color.  The tiny crystals are generally prismatic and elongated along the B-Axis, not the C-axis. These prismatic crystals often occurring in radiating spherules.  The hardness is ~4.5 (Mohs).  How did I identify these ting crystals? I broke off a couple and obtained a yellow streak (I think).  Minerals with a yellow streak are rare.  They also dissolved in hydrochloric acid.  Otherwise is was a wild guess.

Another non-arsenate mineral that popped up in the Ojuela specimens was chalcophanite, a hydrated, zinc-iron-manganese, manganese oxide [(Zn,Fe,Mn)Mn3)7-3H2O].  Again, chalcophanite is a common oxide mineral in polymetallic deposits.  However, it often is difficult to visually (as are many manganese minerals) identify since individual crystals are quite small. Crystals are often platey, soft (~2.5 Mohs), metallic opaque with a color ranging from dark blue to black. These tiny crystals often form a druse-like coating. 

"Clumps" of chalcophanite with green spherules of conichalcite?  Width FOV ~11 mm. 

Perhaps the most beautiful specimen (~10 x 6 cm.) in my mixed box is a combination of gemmy hemimorphite crystals of all sizes and shapes scattered over a chalcophanite matrix.  Hemimorphite is a hydrated zinc silicate [Zn4Si2O7(OH)2-H2O] that occurs in a number of environments, colors, lusters, and for decades was confused with the zinc carbonate, smithsonite [ZnCO3].  The name comes from doubly terminated crystals where the terminations have different faces (hemimorphic development).  The crystals have a white streak, a vitreous luster, ~5 hardness (Mohs), are colorless and transparent to translucent, and come from the oxidized zone of zinc-bearing mineral deposits. With a zinc component of over 50%, hemimorphite is a minor ore of zinc.
Gemmy crystals of hemimorphite scattered on a matrix of chalcophanite with a base of goethite/limonite.
In a photomicrograph these submillimeter "white" acicular crystals are scattered over the chalcophanite.  

On the reverse of the above specimen there is a vug filled spherules of the copper zinc carbonate, rosasite  [(Cu,Zn)2(CO3)(OH)2 ].  Length of vug ~1 cm.
Also on the reverse is another mineral.  A wild guess is scorodite, an iron arsenate [Fe3+AsO4 · 2H2O].

The question, at least one of them, is the identity of some really microscopic mineral aggregates situated on the spherules of chalcophanite.  At one time or another I thought perhaps cerussite, hemimorphite, pyrolusite (but needles are not black), ojuelaite, and perhaps others.  It is a tough call and above my pay grade to make it!

I learned much from this little exercise, not the least of which is that submillimeter crystals are very difficult to photograph with my digital camera.  The second is that many arsenates have been discovered in the last 50 years and are relatively uncommon.  The third, life is good: learn to enjoy every minute of your life. Be happy now. Don't wait for something outside of yourself to make you happy in the future. Think how really precious is the time you have to spend, whether it's at work or with your family. Every minute should be enjoyed and savored.
Earl Nightingale

Sunday, September 23, 2018

KANSAS PSEUDOMORPHS: LIMONITE AFTER PYRITE


A couple of years ago, while attending the RMFMS meeting in Wichita, Kansas, a gentleman walked in with a paper bag and approached a dealer where I was examining a few specimens.  He opened the bag and asked the dealer if he could help identify his rocks.  Being curious, I stayed around to look at “what was in the bag.”  To my surprise, he dumped several nice mineral octahedrons on the case and said he found them along a “draw” over in Marion County.  Well, this really piqued my interest since mineral crystals are not all that common in Kansas—except for the Tri-State Lead and Zinc District in the southeast part of the state.  My initial guess, without handling the specimens, was weathered magnetite.  I hustled away to locate a magnet and a loupe from a friend but alas, when I returned, the sack was “gone” and the dealer said the specimens were purchased by “someone.”  So that tale ended there on the Kansas prairie.
A generic octahedron mineral belonging to the Isometric System.  Crystals in this System have three axes of equal length meeting at 90 degrees, labeled below as axes X+ X-, Y+ Y-, and  Z+ Z-.  Diagrams courtesy of metafysical.nl.


Upon returning home I could not find evidence of larger specimens of magnetite that had been found in Kansas.  A few small octahedrons are present in the kimberlites north of Manhattan and the “black sands” found in western Kansas streams usually contain tiny magnetite grains (detected by a magnet).  That was about it until I ran across a reference to a small article published by A.C. Carpenter in the 1941 Transactions of the Kansas Academy of Science, New Mineral Localities in Kansas


Although small octahedrons of limonite pseudomorphs after magnetite or pyrite have been found in Kansas for at least 50 years [late 1880s], definite localities where they found be located remained unknown.  All known collections either bore the label “from Kansas” or else carried the name of a county as McPherson, Dickinson, and Marion. Last New Year’s week I…found a number of octahedrons of limonite pseudomorphs on the John Reimer farm in sec. 12, T. 18 S., R. 4 E., 1 mile north and 1 ¼ miles east of Lincolnville in Marion County…A second locality is reported to be near Roxbury in McPherson County.  
 
 A glance of the Kansas Geological Survey’s selection of county geologic maps indicates that Marion County does not have a county report nor county map.  Therefore, the larger scale State Map was used to place the collecting locality in Permian strata, probably rocks of the Sumner Group (redbeds and evaporite).  In addition, Carpenter noted that additional limonite pseudomorphs were reported (no reference) “to be near Roxbury.”  That small town is in northeastern McPherson County, east of Marion County, where a small sliver of Sumner Group rocks, maybe the lower formation (Wellington) crop out along a creek.  That is my best guess; however, I cannot locate references describing pyrite (or limonite) in these rocks.

Mindat.org believes that limonite is probably not a recognized mineral name but is used for unidentified massive hydroxides and oxides of iron, with no visible crystals and a yellow-brown streak.  Limonite is most commonly the mineral goethite (FeO(OH).  Chemically, limonite is Fe,O,OH,H2O or Fe,O(OH)-nH2O.  Pyrite is FeS2and limonite forms during chemical weathering where water hydrates the iron but the original crystal shape of pyrite remains..


One of my former students, living in Kansas, knew I was interested in these Kansas crystals and sent me 2copy of a brochure published by a New York mineral dealer in 1902.  One of the minerals offered for sale by George L. English was LIMONITE PSEUDOMORPHS AFTER MAGNETITE, Kansas.  Excellent ¼ to 3/8 inch octahedrons, 1 dozen for 10c.  Evidently the 1902 brochure came from a 2017 discussion on MinDat (https://www.mindat.org/mesg-7-409374.html) where a consensus was reached that the crystals were limonite after pyrite rather than after magnetite.
Advertising brochure from George L. English.

However, there is more to the story.  The first tidbit is that I recently was rummaging around a rock shop and behold there was a stray octahedron with a label stating, “limonite after magnetite, Kansas.”  It had to be! Yep, it looked just like the newly determined limonite after pyrite crystals pictured on MinDat.  So now, I finally had one of these somewhat elusive Kansas crystals.



Octahedron of limonite pseudomorph after pyrite. Axes are ~1.2 cm.
The second tidbit involves the New York dealer, George L. English. According to the Mineralogical Record Biographical Archive, English was a very famous collector and dealer (certainly more so that I knew). He was born in Philadelphia (1864) and was selling minerals in that city by 1887: “a truly wonderful assortment of Arizona wulfenites, vanadinites, azurites, and malachites in addition to fine Franklin fowlerites.”  He picked up a couple of partners and opened a New York branch 1887 and by 1889 his ad stated, “We deal exclusively in minerals…It is universally acknowledged that we have the finest and most complete stock of minerals in the United States.”  In 1896 English incorporated his company, now completely in New York, and sold 150 shares (at $100 each).  Mr. Lazard Cahn was a member of the Board of Directors. English spent the latter part of his life working for, and with, Ward’s Natural Science Establishment, serving as a consulting mineralogist, evaluating collections and establishing monetary values for minerals, and writing a very popular book entitled Getting Acquainted with Minerals.  He recognized as new minerals penfieldite, graftonite, pyroxmangite, and skemmatite, and referred them to investigators for detailed descriptions. A rare hydrous phosphate of calcium, potassium, and aluminum from near Fairfield, Utah, was named englishite in his honor.  English died in 1944.



Mineral labels, early 1900s, of New York mineral dealers George L. English and Lazard Cahn.  Both from the Mineralogical Record label collection.

Of interest to me, other than the limonite after pyrite octahedrons, was English’s relationship to the founder, and Honorary President for Life, of my home club, the Colorado Springs Mineralogical Society.

Wilson, in the Mineralogical Record Biographical Achieves, noted Cahn began dealing in mineral specimens for pleasure in the mid-1890's from his offices in New York City. Cahn's first advertisement appeared in the Exchange Column of the July 1895 issue of The Mineral Collector. He wanted to buy or exchange for "very choice, well crystallized American minerals," and offered for sale Colorado amazonite and orthoclase twins, rhodochrosite crystals on matrix, bastnasite pseudomorphs, arfvedsonite crystals and pyrite crystal groups. So, by 1896 Lazard Cahn evidently was a well-respected mineral collector/dealer living in Colorado Springs while keeping an office in New York and was invited to join the Board of Directors of the George L. English Company.

I've always loved life, and I've never known what's ahead. I love not knowing what might be round the corner. I love serendipity.  (Twiggy).  So it goes, round and round: Octahedron pseudomorphs---George English---Lazard Cahn---Colorado Springs Mineralogical Society---Mike---Octahedron pseudomorphs!!