Saturday, July 29, 2023

GOEDKENITE AND PALERMOITE: PALERMO #!



If opportunity doesn't knock, build a door.

    Milton Berle

I spent a fair amount of time pondering over how to write a posting on a couple of very unfamiliar minerals. Especially writing about minerals that are so tiny, good photomicrographs (with my equipment) are tough to produce. But I wanted to remove them from my “to do” list. So, with no opportunity presenting itself I built a door, knocked, and waded into the swamp. Welcome to Mike’s cabinet of very unfamiliar minerals!

One of the more famous pegmatite mines in the eastern U.S. is the Palermo #1 Mine near North Groton, Grafton County, New Hampshire, one of the several pegmatites emplaced along the western part of the State. These pegmatite bodies are located in the Acadian Orogenic Belt, a tectonic area that represents the Devonian (~420Ma --~360 Ma) uplift of mountains in the northern section of the Appalachian Orogen, around southern Virginia to Newfoundland. This uplift was the result of plate movement as a microcontinent named Avalonia (parts of Europe) was banging against Laurentia (proto–North America) and being accreted (the terrane was sticking to Laurentia) while the proto-Atlantic Ocean was being subducted under the Laurentian continental plate. Of course, the orogenic event was much more complex than this explanation!

The Grafton pegmatites are a hotbed for finding phosphate minerals, including the Palermo #1 pegmatite where something like 159 minerals with 15 Types, many of them phosphates, have been identified (MinDat.org). The pegmatites within the area of Palermo mine #1 (and mines #2, and #3) are quite complex but have as their primary phosphates triphylite (Li, Fe) AND/OR lithiophylite (Li, Mn), and montebrasite (Li, Al) AND/OR ambygonite (Li, Al, F). These primary minerals then interacted with post-magmatic aqueous fluids to produce several tens of secondary phosphate minerals (Nizamoff, 2006) .

Two of these rare, late-stage secondary hydrothermal minerals from a complex granite pegmatite exposed at Palermo #1 are goedkenite Sr2Al(PO4)2(OH) and palermoite (Li,Na)2(Sr,Ca)Al4(PO4)4(OH)4. Goedkenite, a strontium aluminum hydrated phosphate is the lesser known of the two although they are close allies at the Type Locality as goedkenite was originally found as tiny crystals growing epitaxally and perpendicularly on palermoite crystals (Moore and others, 1975). Goedkenite crystals are prismatic, transparent, colorless, or pale yellow, sub-vitreous, and usually less than 1 mm in length. They have a white streak and a measured hardness of ~5.0 (Mohs). Goedkenite is only known from a couple of areas, the Palermo #1 in New Hampshire, and the Lupka Quarry in Slovakia.


Two larger crystals of palermoite (a V) with microscopic epitaxial crystals of goedkenite.

Two isolated transparent crystals of goedkenite (right center).


Submillimeter transparent crystal of goedkenite (close to center of photo)..


Splintery clusters of palermoite crystals





Submillimeter transparent, prismatic, epitaxial crystals of goedkenite "sprouting" from larger palermoite crystals.

My guess is there is a second growth of epitaxial crystals of goedkenite. The larger palermoite crystal is out of focus on the bottom.

Palermoite, is the better known of the two friends due to its name being derived from the Palermo pegmatite (Mrose, 1953). It is a lithium strontium hydrated phosphate [(Li,Na)2(Sr,Ca)Al4(PO4)4(OH)4], and like goedkenite, is quite rare and only known from three localities, the Type Locality, the Nanping pegmatite field in China, and Toirano in Italy (as noted by MinDat).

Crystals are usually prismatic and splintery, transparent, colorless to white, vitreous, and occur as individuals or clusters of crystals. The mineral has a white streak and a measured hardness of ~5.5 (Mohs). Palermoite crystals are longer that goedkenite but still only a few mm in length (or less).


Unknown. Nice crystal.

 
Unknown.

Unknown green mineral.


Unknown. Maybe phosphosiderite?


Unknown. Could it be foggite??

Nizamoff and others (2022) described the Palermo #1 pegmatite as “a beryl-phosphate pegmatite member of the LCT (lithium,-cesium,- or tantalum-enriched) family and is enriched in phosphorus.

My specimen is a micromount (~1 cm x ~1cm) collected and mounted by John Reiner and then acquired by Art Smith in 1981. Reiner’s (1909-1995) memorial is in Rocks and Minerals, vol. 71, no. 2.


The micromount ~1 cm X ~1 cm. Full of crystals.

                                     REFERENCES CITED

Mrose, M.E.,1953, Palermoite and goyazite, two strontium minerals from the Palermo mine, North Groton, New Hampshire. (Abstract from the 33rd annual meeting of the Mineralogical Society of America): American Mineralogist: vol. 38.

Moore, P.B., Irving, A.J., Kampf, A.R., 1975, Foggite, CaAl(OH)2(H2O)[PO4]; goedkenite, (Sr,Ca)2Al(OH)[PO4]2; and samuelsonite, (Ca,Ba)Fe22+Mn22+Ca8Al2(OH)2[PO4]10. Three new species from the Palermo No. 1 pegmatite, North Groton, New Hampshire: American Mineralogist vol. 60.

Nizamoff, J., 2006, The Mineralogy, Geochemistry and Phosphate Paragenesis of the Palermo #2 Pegmatite, North Groton, New Hampshire: University of New Orleans Theses and Dissertations. 398.

Nizamoff, J.W., R,W. Whitmore, and M.I. Jacobson, 2022, The Where of Mineral Names: Palermoite, Palermo No. 1 Mine, North Groton, Grafton County, New Hampshire: Rocks and Minerals, vol.97, no.3.


Thursday, July 27, 2023

BISMUTH, ITS ELEMENTAL MY DEAR WATSON

 

Does it really contain bismuth? Yep. Bismuth can be used in making scents! Pepto Bismo

Bismuth (Bi) is a metallic element (Atomic Number 83) that has many chemical and physical properties that resemble antimony and arsenic. Although most/many people probably recognize the name bismuth they know very little about the element except that “pink-colored” bismuth (bismuth subsalicylate; C7H5BiO4) is an anti-diarrhea OTC medicine. Waterfowl hunters probably realize that bismuth (86% the density of lead and low metal toxicity) shot is a substitute for lead shot (to prevent lead poisoning) and fishers often use bismuth-based weights for the same reason. Rockhounds and others who attend rock and mineral shows are often exposed to nice hoppered bismuth crystals covered with a rainbow of iridescent colors. These crystals are not “natural” and are synthetic. 

Hoppered synthetic bismuth crystal from Wikipedia attributed to:  Alchemist-hp (www.pse-mendelejew.de) + Richard Bartz

Natural bismuth is extremely difficult for an ole plugger like me to identify.  [Don't be afraid to be confused. Try to remain permanently confused. Anything is possible! G. Saunders]. It rarely occurs as crystals but if so, are often trigonal, reddish white to creamy white tarnished to iridescent pink or yellow and have a metallic luster and a silver streak. Bismuth can be massive and very “dark” in color due to a tarnish. Perhaps the most common habit is foliated and parallel crystals or crystal fragments since it has perfect cleavage. MinDat noted that bismuth occurs in “hydrothermal veins with ores of Co, Ni, Ag, and Sn; in pegmatites and topaz-bearing Sn–W quartz veins.” It is just a tough mineral to ID in rocks unless one is specifically expecting it’s presence.


As best that I can determine this is natural bismuth from the Rubicon Pegmatite in Namibia. Wirth FOV ~1 cm.

The IMS recognizes 128 valid minerals that contain bismuth and sulfur (MinDat, July 21, 2023). The most common sulfide is bismuthinite [Bi2O3], a major ore of bismuth.  It is a very soft mineral [~2.5 Mohs], has a metallic luster with a lead gray to while color, and is opaque. The mineral crystalizes in the Orthorhombic System, but most specimens appear as long prismatic to slender acicular crystals that are often flexible.  With weathering an iridescent tarnish usually is noted.  The crystals are often mistaken for stibnite (Trigonal Crystal System) to which it is related via solid solution—the bismuth being replaced by antimony. In addition, bismuthinite forms a series with aikinite, a lead, copper bismuth sulfide. Bismuthinite, from the famous mines in Bolivia, formed in high-temperature hydrothermal vein deposit or tourmaline-bearing copper veins associated with granite.


Bismuthinite, with some marcasite coating, collected from Farralion Viejo Mine, Cerro Tazna, Bolivia. Width FOV ~ 2.8 cm.


 

Uber reflective partial crystals of bismuthinite.  Non-reflective crystals with a covering of marcasite.  Width FOV ~1.2 cm.

Bismutite, a carbonate [Bi2(CO2)O2], is an uncommon mineral and an oxidation product of bismuth sulfide minerals such as bismuthinite.  My specimen came from Rio Arriba, County, New Mexico, where pegmatites have been mined (mostly for Rare Earth Elements and thorium) from granites of Precambrian age in the Pteaca District. I presume the bismutite is simply a non-important secondary mineral.

Bismutite is a pretty non-descript mineral, at least to me, as the luster ranges from vitreous to dull and the color yellow to black.  Most specimens I have observed, including mine, are yellow-tan earthy mats or plates without observable crystal structures.  However, it does have a gray streak and is quite soft ~3.0 Mohs).  Probably the only way that I might recognize bismutite would be to realize that the hypogene sulfide bismuthinite was present in the deposit.


Yellow fibrous and crystalline bismutite.  Width of photomicrograph ~1.7 cm.

 

At the 2016 Tucson Show I was rummaging through some vendor minerals toward closing time and came upon a specimen of pottsite.  Pottsite is a quite rare hydrated (H2O) lead and bismuth vanadate [(Pb3Bi)Bi(VO4)4-H2O] found in the oxide zones of tungsten-bearing rocks.  MinDat noted that pottsite is the only natural lead-bismuth vanadate known.  The Pb/Bi ratio varies from0.86 to 1.48. At the rock and mineral shows that I frequent pottsite is not a common mineral for sale as the mineral has only been found in five localities (MinDat): Cordoba, Argentina; Bavaria, Germany; USA California, and Nevada, (Churchill and Lander counties).  It seems as if most of the collected specimens come from the type locality, the Linka Mine, Spencer Hot Springs District in Lander County.  The major target at the Linka was tungsten with slight recovery of copper and molybdenum.  Sherlock and others (1996) defined the Spencer Hot Springs District as a “Tungsten Skarn” where scheelite-bearing [calcium tungstate], calc-silicate rocks are formed at boundaries of hot magma bodies (a granodiorite at Linka) and carbonate rocks.  The hot fluids dissolve some of the carbonate rocks (a process of metamorphism called metasomatism) and deposit a wide variety of minerals dependent upon the composition of the hydrothermal fluid.  Evidently at the Spencer Hots Springs District, tungsten was a major component of the fluids along with secondary? lead, vanadium and bismuth.  I remain uncertain as to the rareness of combining lead and bismuth.


The bright yellow material is submilimeter prismatic to stubby crystals of yellow pottsite. The globular orange mineral is likely clinobisvanite. The chalky white mineral may be bismutite that lost the copper component?

Clinobisvanite [Bi(VO)4] is an interesting mineral for several reasons, but especially for the derivation of its name: crystallographic symmetry (monoCLINic) and composition, containing BISmuth and VANadium. It often occurs with pottsite (see above) and in microscopic form is quite difficult for rockhounds like me to distinguish between. I often confuse the tiny “pseudo-tetragonal crystals” of clinobisvanite with the “bipyramids or stubby prisms terminated by pyramids” of pottsite (as described by MinDat). Pottsite is usually bright yellow; however, an orange coating may be present. Clinobisvanite  is yellow, yellow-orange, pale orange, or deep reddish orange in color. Often clinobisvanite occurs as platy or globular aggregates.




Orange to yellow orange clinovisbanite and more pale yellow pottsite from the Linka Mine, Lander County, Wyoming. 

There is another bismuth vanadate thrown into the mix and that is pucherite [Bi(VO4)].  At first glance pucherite may “look like” it’s more common relative vanadinite. My specimen has the same reddish brown to yellowish brown color; however, the well-defined crystals with sharp angles do not have the hexagonal barrel shape of vanadinite but are tabular to equant and sometimes prismatic.  They have a vitreous to adamantine luster, are fairly soft with a hardness of 4 (Mohs), a distinctive yellow streak, a conchoidal fracture and are transparent to translucent. Pucherite and clinobisvanite, at times, occur together such as in one of my specimens from Namibia.  In fact, when reading the literature, I noted that at some localities these two minerals are often confused and with the advent of electronic gizmos the names have been reversed. So what I need is a variety of spectroscopes for Frost and others (2006) stated “both Raman and infrared spectroscopy have been used to characterise the three phase-related minerals—dreyerite (tetragonal BiVO4), pucherite (orthorhombic BiVO4) and clinobisvanite (monoclinic BiVO4)—and a comparison of the spectra is made with that of the minerals namibite (Cu(BiO2)VO4(OH)), schumacherite (Bi3O(OH)(VO4)2) and pottsite (PbBiH(VO4)2·2H2O)… Raman spectroscopy enables new insights into the chemistry of these bismuth vanadate minerals. Raman spectroscopy enables the identification of the bismuth vanadate minerals in mineral matrices where paragenetic relationships exist between the minerals.”



Reddish brown 
submillimeter crystals of pucherite.  Width FOV, top ~1.0 cm, bottom ~5 mm.

Somehow, I acquired another bismuth mineral for my collection: preisingerite [Bi3(AsO4)2O(OH)] is a rare anhydrous bismuth arsenate found as a secondary mineral in the oxidized zone of some arsenic-bearing hydrothermal mineral deposits.  The mineral seems to appear in a variety of colors and habits. Although MinDat seems to favor colors of white to gray to straw yellow, most of their photos, and my specimen, produce green to olive green, rounded to tabular to rhombohedral crystals and crusts. Specimens have a sub adamantine luster, sometimes with a conchoidal fracture, and a measured hardness of 3-4 (Mohs).





Poorly formed green crust on quartz matrix (top) while bottom three photomicrographs show poorly formed green crystals. All are small as the width FOV is ~4mm

Preisingerite, pucherite, and clinobisvanite are well known from the Pucher Shaft, Wolfgang Maaßen Mine field, Schneeberg, Erzgebirgskreis, Saxony, Germany MinDat.org noted the area is a polymetallic deposit (Ag-Bi-Co-Ni-U-bearing veins), was worked for silver and bismuth since the 15th century, later for cobalt and, in the 20th century, for uranium. Most of the veins are hydrothermally formed. The rocks in the field are early Paleozoic and late Precambrian metamorphosed igneous and sedimentary rocks that were intruded by late Paleozoic granitic rocks.  All of this tectonic activity was a geologic mountain-building event caused by the collision of Gondwana and Eurasia to form the supercontinent of Pangaea. These minerals are rare alteration product of other bismuth minerals in the oxidized zone of hydrothermal ore deposits.



Mixite "tuffs" and rosasite "balls" collected from the Carissa Mine, Tintic Mining District, Utah.  Width FOV ~ 1 cm.

The most interesting bismuth specimen in my small collection is mixite, a rare copper bismuth arsenate [BiCu6(AsO4)3(OH)6 · H2O]. Essentially a micromineral, mixite occurs as very tiny, slender acicular needles that often congregate together in tuffs or radial sprays. Although the crystals are usually some shades of green to blue-green, occasionally they are white to light blue.  Individuals appear to have an adamantine luster although this is a difficult call. The tuffs are more silky in nature. Crystals belong to the Hexagonal System and appear to be translucent to transparent.  Hardness is listed as 3.5-4 although that is tough for me to determine. Mixite is a secondary mineral found in oxidation zones of copper-bismuth deposits.

It is best for me to retire from looking at bismuth minerals--unless someone wants to teach me the intricacies of operating Raman and Infrared  Spectrometers!  I am confused!

People just want to know they are not alone being confused! (J. Ames). So good. Be confused. Confusion is where inspiration come from! (R. Mundel).  

 

REFERENCES CITED

Frost, R. L., D.A. Henry, M.L. Weier, and W. Martens, 2006, Raman spectroscopy of three polymorphs of BiVO4: clinobisvanite, dreyerite and pucherite, with comparisons to (VO4)3-bearing minerals: namibite, pottsite and schumacherite: Journal of Raman Spectography, Vol. 37, Issue 7.

Sherlock, M.G., D.P. Cox, and D.F. Huber, 1996, Known mineral deposits and occurrences in Nevada: in Chapter 10 from Nevada Bureau of Mines and Geology Open-File Report 96-2: An analysis of Nevada's metal-bearing mineral resources): www.Nnsa.energy.gov/sites/dsfault/files/nnsa/imlinefiles

 

Monday, July 10, 2023

WAVELLITE & FUELLITE ON THE ROAD TO WINNEMUCCA

 I was totin' my pack along the dusty Winnemucca road

When along came a semi with a high and canvas covered load
"If you're going to Winnemucca, Mack with me, you can ride"
So I climbed into the cab, and then I settled down inside
He asked me if I'd seen a road with so much dust and sand
And I said, "Listen, Bud, I've traveled every road in this here land"
I've been everywhere, man
I've been everywhere, man
Hank Snow version

An army of caterpillars crawling northward.     Clarence Dutton



Google Earth© image of Basin and Range Province around Lovelock, Nevada, and the West Humboldt Range. home of the Willard Mine. The Basin and Range is defined by narrow faulted mountain ranges with adjacent rather flat basins—a horst and graben topography. The topography is due to extensional tectonics (pull-apart) of the later Tertiary (Miocene, ~17 Ma and probably continuing).

The name Willard conjures up a vivid picture of Ben and his rat friends devouring their former human friend Willard! I am not a big fan of Sci Fi or horror films, but Willard is not one to watch before hitting the rack. But 1971 was many decades ago and now the name is much more exciting---a mining district, and mine, located in a desolate part of Pershing County, Nevada, in the north end of the West Humboldt Range not too far from the County Seat of Lovelock. In fact, Lovelock is the only town in this large county. What is the landscape like? Ask Center Divide a group who recorded the album From Lovelock to Winnemucca:

If you make that drive
And you like tunes you better have a tape deck
Airwaves are empty
Ain't a lot on the radio
Better yet you can sit and ride
And listen to the dry wind
Flappin' through the window
Breathe in the scent of sage
Breathe it in real slow
And you breathe deeper
I swear you will

That description of driving across Nevada is one for the ages. Try the drive with a couple of youngsters sometime---been there, done that.

If you ever drive
From Lovelock to Winnemucca
I suggest you stop at every Dairy Queen
Towns are few and they're far between
And you'll have to fill up anyway
And there's something 'bout a frosty
Makes the pain go away

Somewhere near Lovelock is the Willard Mine, or the Willard Mines, all clustered together in the Willard Mining District. The area has a long history of exploration dating back to the early 1900s with most tunnels and shafts producing minor amounts of silver, gold, and antimony until mid-century. Drilling exploration found mineable gold in the 1980s and production lasted for about two to three years from 1990-1993. The initial gold was from near surface free-milling gold and later recouped by heap leaching. The mineralization was in the Late Triassic to Early Jurassic Auld Lang Syne Group (slightly metamorphosed siltstones and limestones). Fractures and brecciation zones in these sedimentary rocks allowed for gold- and silver-bearing hydrothermal solutions, associated with Tertiary intrusive rocks, to spread throughout. I could not locate production figures; however, exploratory drilling continued into the early 21st century but today mandatory remediation has covered much of the area.

So, other than there's a whole lotta room to lose a broken heart (Center Divide) what else is neat about the area? Well, for starters a 1905  paleontological expedition led by John C. Merriam of UC Berkeley found a substantial number of Ichthyosaurs (Mesozoic marine reptiles), Cymbospondylus petrinus, and transported most back to the UC Museum. Twenty fives years later even larger and better preserved Ichthyosaurs, Shonisaurus popularus were located in nearby Nye County that later became Berlin-Ichthyosaur State Park.  More importantly for this Post, there are 41 mineral species known known from the Willard (MinDat) and the mine “is the site of the world's largest crystals of fluellite and perhaps also minyulite; and it has furnished what are by far the finest quality specimens of wavellite, fluellite and minyulite ever discovered in the state [Nevada]… along with other minerals including… crandallite, dufrenite, gypsum, jarosite, native selenium and strengite/variscite” (Jensen and others, 2001). It is a treasure trove of spectacular supergene phosphate minerals in a sediment-hosted, epithermal, Carlin-type gold deposit. (See Blog Post on Carlin Deposits August 19, 2020).

Over the years I have picked up Willard specimens of fluellite (mineral was unknown to me) formerly in the collection of Robert Pederson, and wavellite (it was not green like Arkansas) formerly in the collection of Jim Thow--- or Jim Thon---?




                  



-

Transparent fluellite crystals on top of quartz crystals. Largest crystal, top microphotograph is ~1 mm in width. Most are submillimeter. 

Fuellite crystals at Willard (at least in my specimen) are colorless, transparent, sharp, mirror-lustrous, euhedral, orthorhombic crystals. A few other localities may produce lavender or yellow crystals. Fluellite is a  rather rare fluoro-hydroxyl, secondary, phosphate [Al2(PO4)F2(OH)-7H2O] that is usually associated with pegmatites and phosphorite deposits. At Willard, fluellite is found in a supergene phosphate zone and is paragenetically late and often occurs directly upon lustrous quartz crystals. “These are very likely the best and largest examples of the species found in the world” (Jensen and others, 2001). 

Microphotographs below show numerous radiating clusters of clear to white  fibrous crystals.  Most are 1-2 mm in size although some are submillimeter.





 
Submillimeter pyrite.
Chalcedony-like mass of what I presume is wavellite--note striations. The dark flakes might be native selenium?
Hexagonal molds left by quartz crystals (epimorph?)

Although I usually associate wavellite as a green mass (colored by vanadium) of radial crystals found in Arkansas, the wavellite specimens in these phosphate rocks of Nevada are completely different. The Willard wavellites are radiating clusters of clear to white (no vanadium) fibrous crystals in a delicate  “jackstraw” type of arrangement. Almost hidden away among the fibers are scattered, quite tiny, pale gray to white wavellite spheres. Wavellite [Al3(PO4)2(OH,F)3·5H2O] is also found in the phosphate supergene. “Paragenetically, wavellite occurs either on quartz or the phosphates crandallite, and/or variscite” and are easily ranked as the finest examples of wavellite ever found in Nevada” (Jensen and others, 2001).

But really confusing to me is that recently (Kampf and others, 2017) described fluorwavellite [Al3(PO4)2(OH)2F·5H2O] as the F analogue of wavellite. It is visually indistinguishable from wavellite, since it is essentially identical to wavellite in appearance and physical properties. It has the same structure as wavellite, differing only in having one of the two independent hydroxyl sites replaced by F. Therefore, MinDat at about the same time, noted that the Willard wavellite is actually fluorwavellite distinguishable only with the use of electronic gizmos. Way above my pay grade!

REFERENCES CITED

Jensen, M., J. Leising, 2001, Wavellite, fluellite and minyulite from the Willard Mine, Pershing County, Nevada: Mineralogical Record vol.32, no.4.

Kampf, A.R., P.M. Adams, H. Barwood, B.P. Nash, 2017,  Fluorwavellite, Al3(PO4)2(OH)2F·5H2O, the fluorine analogue of wavellite: American Mineralogist 102.

ALSO see:

Conelea, R. and W.C. Howard, 2010, The geology and gold-silver mineralization of the Wilco Project—Willard Mining District, Pershing County, Nevada in Great Basin Evolution and Metallogeny: 2010 Symposium Proceedings of the Geological Society of Nevada.

AND REMEMBER:

If you ever drive
From Lovelock to Winnemucca,
It's a good idea to pack your cares along
The desert's big and wide
Those mountains stand far apart.