VANADINITE: MYSTERY MINERAL OF THE BLACK HILLS

                                     Colorful autumn

A yellow tree exploded

surrounded by rocks  

I am starting this post with a question thinking that someone may have the answer! What happened to a four-to-five-ton mass of vanadinite mined in the Black Hills of South Dakota in the late 1800s?  My answer:  I don’t have the slightest idea but would like to find out!

OK, I will start at the beginning.  I have a specimen (shown below) with hundreds of very tiny, prismatic crystals of vanadinite with an older label stating: Vanadinite, Richmond Mine, South Dakota.

Thousands of tiny prismatic vanadinite crystals are embedded in this specimen along of gray manganese a colorless lead mineral, perhaps cerussite. A USA dollar coin is used for scale and the maximum width of the specimen is ~8.3 cm.

 

Photomicrographs of mass of vanadinite crystals. Crystal length is on the order of ~1 mm or less.

Manganese oxide and vanadinite.

Vanadinite and unknown patch near the center.  The yellow material in lower left may be mimitite. 

Now most rockhounds have a specimen, or 20, of vanadinite in their collection. The mineral is a lead chlorvanadate [Pb₅(VO₄)₃Cl] with hexagonal crystals, various color hues of red to orange to brown, less than adamantine in luster, and soft at ~2.5-3.0 in hardness (Mohs).   It forms a solid solution with pyromorphite (lead chlorophosphate) and mimitite (lead chloroaresnate). MinDat notes vanadinite is a secondary mineral found in the “oxidation zone of lead deposits in arid climates resulting from the alteration of vanadiferous sulphides and silicates of the gangue and wall rocks.”  Due to color and crystal shape, vanadinite is a very collectable mineral.

So, readers now have a new little chore. Use a web browser to locate specimens, MinDat is ok, of vanadinite from say Arizona. You will find there are too many localities and photos to count. Now browse for vanadinite in South Dakota and what do you find?  I count 1 photo and 5 localities, and a couple of those may be suspicious. So, what happened to such a large hunk of vanadinite mined in the 1880s?

This story all started with Lt. Col. George Custer, on July 2, 1974, “marching” out from Fort Abraham Lincoln (located across the Missouri River from Bismarck, North Dakota) with somewhere close to 1200 men.  Besides members of 10 companies of his 7^th Calvary (including a 16 piece band), the group included ~110 wagons and accompanying teamsters, about 300 head of cattle for food in case the hunters could not produce game, a medical staff, several newspaper correspondents, the experienced miners Horatio Ross and William McKay (perhaps disguised as teamsters), several Native American Scouts, at least two of Custer’s staghounds, extra horses and mules, Chief Engineer Captain William Ludlow and his assistant (who produced wonderful maps), and Scientist George Bird Grinnell, a graduate student at Yale who later became a famous anthropologist, naturalist and writer, assigned to describe the flora and fauna.  Grinnell had three assistants: 1) Newton H. Winchell later became the Director of the Minnesota State Geological Survey and authored the six volume treatise entitled The Geology of Minnesota; 2) Luther North, a jack-of-all-trades best remembered for leading a group of Pawnee Scouts, along with his brother Frank, helping protect the Union Pacific Railroad and later business partners with William (Buffalo Bill) Cody; and 3) A.B. Donaldson, a botanist and newspaper “man” from Minnesota.  William Illingworth, the Expedition’s photographer, evidently was hired by Ludlow to provide photos for the U.S. Army.  The Expedition also included  at least one woman; a former slave known as Aunt Sally who cooked for Sulter John Smith.

The official record for the trip was a “military reconnaissance of the Black Hills of the Dakota Territory.”  Unofficially, the military wanted to: 1) find ways to subdue the remaining Native Americans in the Black Hills and Powder River Basin; and 2) locate gold so that an unstoppable stampede of miners would head to the Black Hills (see #1). The military and President Grant succeeded although George Custer was less successful personally.

Minor amounts of gold were found in the area along French Creek in the southern part of the Hills (near the current town of Custer).  Just a few flakes, along with the newspaper press, were enough to bring the masses. However, gold mining in the Custer area was never really very successful although many cubic yards of soil and gravel were turned over and panned or sluiced for the metal.  In time the early miners, as well as new immigrants, spread throughout the Hills looking for a miracle of yellow gold.

Several early mining communities started to spring up in the northern Black Hills with the most famous being those mines located near Deadwood and Lead. Several other mining districts were located south and southeast of Spearfish, and I described the Maitland Mining District (Garden District) along False Bottom Creek (posting on October 22, 2016.  The earliest mining activity at Maitland started in the 1880s; however, the major production of gold and silver commenced in 1902 with the opening of the principal Maitland Mine.  In 1942 the Maitland was closed (due to the country’s effort in WWII) but had produced at least 176,000 ounces of gold.  The mineralization is a replacement gold deposit in the quartzite and dolomite units of the Deadwood Formation (Cambrian-Ordovician) with mineralizing fluids associated with nearby Tertiary intrusions. 

Today there is a small cluster of homes (not the originals) located in the Maitland community. There is also a side road, named either the Carbonate Road or the False Bottom Creek Road, trending west to the old mining area of Carbonate Camp.  The name comes from ore mineralization in the middle Paleozoic Pahasapa Limestone rather than from the Deadwood Formation.

In the Carbonate District, the Pahasapa was also intruded extensively by Tertiary sills and dikes. Wimorat and Patterson (2007) noted two different types of ore bodies at Carbonate: 1) fissure veins with gold-bearing iron gouge in the center and lead-silver rich (galena, cerussite, and cerargyrite) mineralized jasperoids (silica) along the margins; and 2) solution cavity-filling ores that are usually closer to igneous intrusions, are less siliceous than jasperoid, and are rich in lead and silver with minor gold.

The major minerals produced at Carbonate were silver, lead and minor gold with the best production for less than 20 years from ~1880-1900 (peak years 1885-1891). In 1885 the Iron Hill Mine, the largest of the Carbonate mines, began to produce gold, silver and lead, and a smelter was constructed. By 1891 the mine had produced $667,000 worth of ore (I presume by 1891 prices). However, Shapiro and Gries (1970) stated that “incomplete records indicate a production of more than $1 million in silver, gold, and lead [from 1881 to 1891].” Other smaller mines in the area included the Adelphi (the largest Carbonate Mine before 1890), Seabury-Calkins, Cleopatra, Pocahontas, Union Hill, Spanish R, and Richmond Hill. But by 1892-93 the town was about played out. Declining silver prices was the big killer; however, a massive degradation of the roads to “civilization” struck a big blow. Today historians remember that in the late 1880s Carbonate Camp was a booming town with hundreds of residents, numerous businesses, including banks, newspapers, stores, mills, smelters, saloons, the Black Hills Hotel, the largest hotel in the Dakota Territory, was three stories high and housed a saloon and banquet room.

The mines at Carbonate kept plugging away and tried, several times, to “make a go of it.”  Irving (1904) stated that “within the last year [actually 1887 according to Parker and Lambert, 1974)] a small 85-ton cyanide plant has been erected to treat the tailings from the old smelter.” A short lived second cyanide mill (I think) was built in 1900-01 and named the Cleopatra Mine Mill (Bureau of Mines staff, 1954).

After the turn of the century some off and on exploration and mining continued at Carbonate Camp, especially at the Iron Hill Mine where the dumps were reworked from 1901-1910.  However, around 1920 exploration hit a snag when the mine flooded and projects were stopped.  Like a Phoenix, Carbonate Camp arose from the ashes and was ready to try again when in 1937 Carbonate Consolidated Mining Company, Inc. acquired the mine; however, I could no longer locate production figures (Bureau of Mines staff, 1954) so the old bird must have bitten the dust (The Phoenix is an immortal bird associated with Greek mythology, with analogs in many cultures, that cyclically regenerates or is otherwise born again. Associated with the sun, a Phoenix obtains new life by arising from the ashes of its predecessor [Wikipedia accessed 19 October 21]).

The Cleopatra Mine never did produce much and Bureau Mines (1954) reported mineral values of ~$200,000—some time prior  to 1910. The host rock at Cleopatra was different from that at Iron Hill since replacement was in the Cambrian Deadwood Formation (as at Maitland).

The Adelphi Mine, of which I have no production figures or history, had ferruginous jasperoid, manganese oxide, galena, and argentiferous cerussite replacing the Pahasapa Limestone. Some of the crevices and fractures associated with the ore had “high gold values” (Bureau of Mines staff, 1954).

The Seabury-Calkins Mine and the Segregated Iron Hill Mine are close to the Adelphi Mine, and with the Spanish R, were also acquired in 1937 by the Carbonate Consolidated Mining Company, Inc.  No production figures are available for the first three, but the Spanish R had $50,000 of production before 1904 (Bureau of Mines, 1954).

It is hard to find production figures for the total mines at Carbonate Camp; however, Shapiro and Gries (1970) stated that in the peak six years the various mines produced 83 ounces of gold [Carbonate Camp was not a major gold producer],18,511 ounces of silver, and 83,191 pounds of lead. 

Irving (1904) described the mining geology and minerals in the Carbonate Camp as follows: The country rock that carries the ore in the Iron Hill mine (more on this later) is the gray Carboniferous limestone (Pahasapa Formation) in which sills, dikes, and irregular masses of  porphyry have been intruded.  The ore bodies are of two kinds: large irregular bodies of lead carbonate, which pass in places into more or less unaltered galena, generally in close contact with the porphyry masses: and partially filled crevices which resemble in a general way the verticals of Ragged Top (a nearby mining district).

[At the Iron Hill Mine] the ore was a large mass of argentiferous lead carbonate (cerussite with silver) which extended down for 800 feet on the east side of a thick dike of fine-grained porphyry.  Much galena was also found with the carbonates, and after the ore was worked out a seam or vertical was detected downward from the main mass.  Other pockets of ore were also found at different points, and in one place a pocket of vanadinite containing 4 or 5 tons was encountered. [Minerals identified from the Mine] included galena, cerussite, cerargyrite, matlockite, wulfenite, pyromorphite, plattnerite, atacamite, and vanadinite.”

But what about vanadium value?  One would think that a 4-5-ton mass of vanadinite would be processed, and production numbers and monetary value would appear--somewhere?  Or would it be?

The element vanadium was first discovered in 1801, rediscovered in 1831, and isolated and produced in 1867.  I don’t know what happened after that date but the first widespread industrial use for vanadium was to harden steel for use in cars, including the early Model T Fords, in the first decade of the 20^th Century. Today, besides the steel alloys, vanadium is used as a catalyst for the chemical industry, in the making of ceramics, glasses, and pigments, and perhaps in the most exciting new use- in vanadium redox-flow batteries for large-scale storage of electricity.  Would the country need vanadium in the ~1890s?  Was it even being produced/processed? I don’t really know as the earliest production figures I can locate were from 1901 when the U.S. produced a whooping 6.8 tons of vanadium and imported “nothing.”  I remain uncertain as to the use of vanadium ~1900.

VANADIUM STATISTICS
U.S. GEOLOGICAL SURVEY
[All values in metric tons (t) vanadium content unless otherwise noted]
Last modification: November 20, 2019
Year	Production	Imports	Exports	Stocks	Apparent consumption	Unit value ($/t)	Unit value (98$/t)	World production
1901	6.80	NA	NA	NA	6.8	NA	NA	NA

 

So perhaps the 4-5-ton hunk of vanadinite was stuck in a stamp mill and then processed for a more useful economic mineral like silver?  This is one of life’s little mysteries that continue to nibble away at inquiring mines.  I do know that specimens of vanadinite from South Dakota are quite rare and this little factoid is what spurred me on to spend tens of hours reviewing what literature I located.

Vanadinite is rarely mentioned in the literature describing South Dakota minerals, or in the big picture where vanadinite is described on a world-wide basis. Campbell and Roberts (1985) noted that the dumps at the Iron Hills Mine yielded the endlichite variety of vanadinite occur[ing] as pale brown, slender prismatic crystals up to 1 cm long, in attractive groups. Thick yellow to orange-yellow botryoidal crusts of mimetite are often associated with vanadinite. Smith and Fritzsch (2000) stated the Carbonate Consolidated Mines (would be the group consolidated in 1937) produced specimen(s) of vanadinite. But again, I could not locate photographs. The same goes for Baldwin (1904) reporting vanadinite from the Spanish R, a point no other website nor research paper noted (except a single statement in Shapiro and Gries {2000} simply quoting Baldwin). The best description of Carbonate Camp vanadinite is from Roberts and Rapp (1965): Vanadinite is a secondary mineral found in the oxidized zone of lead deposits in the Black Hills…A large mass of vanadinite, weighing between four and five tons…was mined from the Iron Hill Mine, Carbonate, during the silver mining operations in the late 1880’s. The vanadinite occurred in small and slender prismatic crystals (SDSM&T-3326), often hair-like in fineness, of a light brown color and up to ½ inch in length. The Geology Museum at South Dakota School of Mines was kind enough to send me photos of that particular specimen and those answer one of my questions about any additional specimens.  I am convinced that most later authors mentioning the Iron Hill vanadinite did not have newly discovered specimens but were simply noting the Museum specimen; however, I could be wrong.

South Dakota Mines Museum of Geology vanadinite specimen SDSM&T-3326.

As best that I can tell, there is at least one vanadinite specimen from the Richmond-Sitting Bull Mine in the Galena District since a photo is shown on MinDat (by Stephen Fritz). However, Smith and Fritzsch (2000) noted vanadinite from the Queen Mine at Galena rather than the Richmond-Sitting Bull Mine as did Roberts and Rapp (1965) who were evidently following an earlier paper by Connolly and O’Harra (1929). This latter paper was unavailable to me. I should also point out that the Richmond-Sitting Bull Mine (Galena District) is not the Richmond Hill Mine at Carbonate Camp.  

MinDat also noted the presence of vanadinite (sparingly) from the upper part of the Spokane Lead Mine in Custer County (Ziegler, 1914), but again additional information or photos were not provided.

In addition, the Rainbow #4 Mine in Custer County (one of my favorite sites) was listed in MinDat as reporting the presence of vanadinite.  However, Smith and Fretzsch (2000), and Lincoln Page (1953) who described the locality, did not mention the mineral.

So, that is about the story I have on vanadinite occurrences in South Dakota: 1) vanadinite is rarely found in mines of the Black Hills; 2) a four to five ton mass of vanadinite was mined in the late 1880s from the Iron Hill Mine in the Carbonate Mining District; 3) I don’t have specific information on the fate of this large mass; 4) a vanadinite specimen displayed in the Geology Museum of the South Dakota School of Mines may have come from this mass; 5) the Richmond Hill Mine is part of, or next door to, the Iron Hill Mine; 6) Tom Loomis of Dakota Matrix was able to identify my specimen as coming from the Iron Hill Mine; 7) it seems reasonable to believe that my specimen of vanadinite may have part of that large mass, perhaps not; 8) photos of vanadinite specimens from South Dakota are essentially nonexistent; 9) the Black Hills are home to several mines that have produced the lead minerals cerussite and/or galena—could these mines contain vanadinite; 10) writing this posting has been like composing a mystery novel!

But wait, there is more.  Remember that the Carbonate District and especially the Iron Hill/Richmond Hill Mine “died” a century ago, or did it?  Remember the Phoenix coming back to life?  In 1988 the State of South Dakota gave a permit to LAC Minerals to operate a surface gold mine on 400 acres associated with the Richmond Hill Mine.  LAC evidently had taken an interest in the area and decided a Tertiary breccia pipe that had intruded into Precambrian rocks contained mineable amounts of gold.  Yep, gold--the old Carbonate District was notorious for giving up miniscule amounts of gold and now LAC was going after the metal in a big way.  Geologists were interested in the gold bearing sulfide minerals and therefore needed a large open production pit (most early Carbonate mines were underground) and heap-leach pits to extract the commodity.  In order to satisfy State requirements about acid mine drainage in a rugged area LAC built the processing facility (the crusher and pits) about a mile and a half from the main production pit. And away they went producing 172,000 ounces of gold in four years.  Not bad.

And then the Phoenix came crashing down in1992 when a 3.5-million-ton waste pile started leaking acidic waters (~3.5 pH), along with heavy metals, into a natural waterway.  It seems as if the waste rock contained a high percentage of marcasite that, when exposed after mining, oxidized quite rapidly.  These chemical reactions are exothermic and heat in the piles was generated (up to 180 degrees F).

All of this action in the waste pile created a flurry of activity within LAC and the State Board of Minerals and Environment with immediate short-term remediation leading to long term stability, mine closure, and post-closure monitoring and land uses. Today remediation activities continue on as-needed and monitoring is still active. Will the Phoenix arise at some time in the future a carbonate Camp?

Above information on the LAC mine was derived from Durkin (1995).

I owe a great deal of thanks to Tom Loomis of DakotaMatrix.com for his advice and identification on my specimen of vanadinite, and to Emily Berry, Assistant Director, Museum of Geology South Dakota Mines, for sharing photographs of the Museum’s specimen of vanadinite.

REFERENCES CITED

Baldwin, G. P., 1904, Black Hills illustrated: Black Hills Mining Men's Association, Publisher unknown.

Bureau of Mines staff, Region V,1954, Black Hills mineral atlas, South Dakota: Part 1: Information Circular 7688.

Campbell, T.J. and W.L. Roberts, 1985, Mineral localities in the Black Hills of South Dakota: Rocks & Minerals, v. 60, no. 3.

Connolly, J. P., 1927, The Tertiary mineralization of the northern Black Hills South Dakota School of Mines Bull. 15.

Durkin, T.V., 1995, Acid mine drainage: reclamation at the Richmond Hill and Gilt Edge Mines, South Dakota: www.envirominecom/case-hist/richmondhill/chl.html.

Page, L. R., and others, 1953, Pegmatite investigations 1942-45, Black Hills, South Dakota: U.S. Geol. Survey Prof. Paper 247.

Parker, Watson and H.K. Lambert, 1974, Black Hills ghost towns: Chicago, The Swallow Press.

Sinclair, Kelesy, 2018. Exploring Black Hill’s hidden ghost towns: Carbonate: BHVisitor.

Smith, A.E. and E. Fritzsch, 2000, South Dakota: Rocks and Minerals, v. 75, no. 3.

Wimorat, M. and C.J. Paterson, 2007, Carbonate-hosted Au-Ag-Pb deposits, northern Black Hills in Paterson, C.J. and A.L. Lisenbee, Metallogeny of gold in the Black Hills, South Dakota (T.B. Thompson, Ed.): Society of Economic Geologists Guidebook Series Volume 7.

Ziegler, V., 1914, The minerals of the Black Hills: South Dakota: School of Mines Bull. 10.