THUNDERCLAPPERS, MERCURY, AND UP AGAINST THE WALL

Yeah, gettin' by on gettin' by is my stock-in-trade
Living it day-to-day, picking up the pieces wherever they fall
Just lettin' it roll, lettin' the high times carry the low
Just living my life easy come, easy 

 Gettin" on from a 1993 album. How is this album related to the mineral mercury? 

In my undergraduate mineralogy class I learned, as a matter of curiosity, that a student could use a blowpipe and Bunsen burner on pieces of cinnabar (HgS) and produce droplets of a silver liquid—native mercury. That little tidbit has stuck with me for over 60 years and was one of the “things” that really turned me on to geology. I also learned, in a chemistry class, that one could partially “dissolve” a copper penny in nitric acid and “slim it down”. Take some mercury, it seemed very common in the chem lab, and caress the slimmed down penny and presto, one had a penny that resembled a dime. The more adventurous students would then use the new coin in the ten-cent soda machine and out popped a bottle of R.C. Cola! Yep, that is what I learned in “college”--just gettin' by on gettin' by...Just lettin" it roll.

Thirty years down the road I was doing early morning decanal work in my office in Missouri and wondered about the wail of approaching emergency sirens. Oh boy, they pulled into my territory—Science Hall and here came the emergency horns/sirens booming out in the Hall itself and students wearily heading out the doors (most faculty just hid in their offices). I thought, “oh crap, a student is ticked off at their professor and is going to blow up the chem lab.” About that time in came, not the SWAT team, but the boys and ladies in their space suits. It turned out that one of the lab students dropped an old mercury thermometer on the floor and some droplets of mercury spilled out. One of the space suit boys said something like, “how dangerous is it? What do you think we out to do?” As I nabbed a pair of gloves, I said, “grab that heavy, small plastic bag and follow me.” I walked over to the broken thermometer, reached down and grabbed it, and dropped it in the bag, All I could spot was three mercury droplets on the floor, so I corralled them on a sheet of paper and then into the bag. I told the space suit guys to turn off that stupid alarm and go back to the station and have a cup of coffee. I took the bag down to the storeroom and told the attendant to put this mercury into the vault and immediately round up the remainder of the mercury thermometers for disposal. We had been working slowly on their disposal since it was a fairly expensive proposition. I returned to my office, wrote up the required report, and stuck a note into my file labeled The Life of a Science Dean.

Another 30 years down the road and I was still playing with mercury! I had pulled out a mount containing mercury and decided a better “look see” was in order. The mercury mineral in the specimen was calomel, a mercury chloride ([Hg₂]Cl₂). It seemed to fit in with the my other mercury related Blog posts: montroydite (12-21-23), galkhanite (11-24-23), rouxelite ((3-4-23), tiemannite (12-10-22), luanheite (12-10-22), cinnabar (3-7-22), schuetteite (3-30-20), coloradoite (1-10-21), kleinite (11-27-19), laffittite (2-26-19).

Calomel, the mercury chloride, is one of the best-known minor mercury minerals due to its use in thunderclappers. More on those later. Mercury occurs in two different oxidation states plus Hg elemental mercury: + 1 Hg or mercurous mercury; +2 Hg mercuric mercury. A note here: the +1 mercurous mercury always occurs, as a chem buddy tried to explain, as a dimer where two identical mercury molecules are joined together by weak bonds. Therefore, the monovalent mercury is written as Hg₂⁺⁺ and is different than the bivalent mercury Hg⁺⁺. So, out of curiosity, I asked about the difference—physical properties are different, chemical reactivity is different, there is a difference in stabilities. "OK, that’s good for now", I whimpered. My friend is a physical chemist, and those scientists live in an alternate world.

Mercury++ is the most common oxidation state in nature and Mercury+ dimers producing compounds are rare. However, the mercurous mercury compound Hg₂⁺⁺Cl₂ is the most common monovalent compound and is known as the mineral calomel or mercury chloride. I know, confusing. The most common mercuric mercury (Hg++) in the rockhound world is the mineral cinnabar (HgS), mercury sulfide. In cinnabar the metal mercury has a charge of ++ and the non-metal sulfur a charge of - - so cinnabar comes out as HgS. Probably just as well that: 1) I dropped out of chemistry after three semesters and did not have an opportunity to take P Chem; and 2) my career did not involve any sort of “teaching” chemistry other than elementary and cursory discussions in Geology 100.

Calomel, like most mercury minerals, can be very difficult to identify, especially in small mounts. Most of the ole pluggers like me use color and collecting locality as major parts of our sleuthing to make reasonable identifications. Mineral identification books and web sites tell me that calomel may be gray, white, yellow white, yellow gray, ash gray or maybe brown in color. Not much help here. Like many mercury minerals, if calomel is exposed to light (sunlight as well as lights in a home or office) the mineral darkens. According to MinDat the darkening is likely due to the formation of nanoparticles: see (https://mineralcare.web.ox.ac.uk/article/cinnabar). That tidbit is for trivial information but is of little help in identification. Now, perhaps here is a winner-the monovalent mercurous mercury minerals turn black when they come into contact with ammonia. OK. Maybe some help here.  As for close relatives to help with identification, calomel is a member of the Calomel Group along with kuzminite. a mercury bromide chloride and moschelite, a mercury iodide. Whoda would have guessed that tidbit? Not much help here!

So now we move on to collecting locality, local geology, and MinDat descriptions. The calomel specimen in my collection (Ex, Mineralogical Research Com.) was collected from the Mariposa Mine, Terlingua, Texas. Anytime one hears the name Terlingua they think of nowhere West Texas, gateway to Big Bend, mercury mines, a ghost town, the Starlight Saloon, and Jerry Jeff Walker.

The Terlingua Mining District has a fantastic collection/remnant of the mercury mines and mining era artifacts scattered across the desert. For a great story see Chasing Quicksilver History in Beautiful Big Bend published in Texas Highways (October 15, 2017). The District is also the third-largest mercury producing area in the United States although it has been shuttered since 1973. According to MinDat, 50 valid minerals are known from the District including nine Types (the Type Locality). All Types are mercury minerals and include one of my favorite names—terlinguacreekite. In addition, seven other mercury minerals (non-Types) are known from the District including the major elemental mercury producer, cinnabar. So, the mines at Terlingua are full of, well maybe just contain, numerous mercury minerals.

Cinnabar was known, and used by, Native Americans (body ornamentation and pictographs) centuries before the arrival of prospectors and miners in Terlingua. According to the local sources, cinnabar produced the first flask of mercury (76 pounds) from Terlingua in 1884. From that date until the early 1970s mercury was produced from several (? 25-40) mines. The boom periods seemed to be right before, after, and during WW I, and then during WW II. After the War some war-torn European countries dumped large amounts of mercury into the world markets and greatly depressed prices. In Texas mining expenses overpowered income and most mines shut down. For the next 25 years various mines would start production for a year or so and then close down and by 1973 the last production ended. 

My specimen of calomel is quite small and found in a vug appearing in white crystalline calcite. The crystals are pale red in color but have darkened considerably to a dark cherry red. They appear to be small tabs and elongated “rectangles” with some being completely encased in calcite. The pale red crystals have a subdued resinous luster while cherry red crystals have a shiny subvitreous luster. Hardness and streak are impossible to determine. Mineralogical Research placed a sticky arrow on the specimen that pointed to, and specified, calomel.

A vug in the crystalline calcite filled with calomel. Width calomel FOV ~2 mm.

There are a few scattered submillimeter splotches and smears of red material on the calcite including some very small prismatic crystals. I am guessing commancheite, a complex mercury oxychloride-bromide:

 Hg²⁺₅₅N^3-₂₄(NH₂,OH)₄(Cl,Br)_34.  However, I would not bet the farm on that identification, but the Mariposa Mine is the Type Locality for that very rare mineral.

Commancheite? Photomicrograph FOV ~2 mm.

As for thunderlappers, many decades ago in a small grade school in central Kansas students spent many hours studying U.S. history, and especially the history of the late 1700s and the formation of the United States. At least we learned about history as the “facts” were presented in the 1950s. As a young student at that time, I was fascinated by events around and during the Revolutionary War, including the construction of the Declaration of Independence. I tried to write like John Handcock and poured over the signers wondering if I had any long-lost relatives on that list. Later in life I was able to trace my lineage back to a man named Francis Cook who actually came to this country on the Mayflower in 1620. Later heroes include one Stephen Percival who is listed as a member of the Cumberland County Milita—Hatch’s Company of Minute Men [New York] during the Revolutionary War. So, no signers of the Declaration (but signed Mayflower Compact) but one James Percival who once heisted a small boat and ended up paying a hefty fine, one who served his country by fighting in the War of Independence, and one Elizabeth Morse, AKA Witch of Newbery, who was convicted of witchcraft in the 1690s.  So now I know the source of some of my traits.

Now, back to a Physician by the name of Benjamin Rush who was a signatory on the Declaration of Independence. He was a Pennsylvanian delegate to the Continental Congress and lived in Philadelphia. Rush was married and the father of 13 children. During the War Rush served as the Surgeon General of the Continental Army and after the War worked in a large variety of positions but seemed most happy teaching students about medicine and chemistry. He also tutored Meriwether Lewis before his journey with William Clark in the Corps of Discovery Expedition as Jefferson wanted Lewis to be the Corp’s “medicine man.” Rush and Lewis constructed a medical supply bag that included 50 dozen doses of the patented Dr. Rush’s Bilious Pills. These little pills contained over 50% mercury and were an “explosive” laxative, hence the common name of thunderclappers. The men of the Corps consumed, by necessity, a diet rich in meat and crappy water and therefore suffered “stomach distress.” So, they often resorted to the thunderclappers as a means to loosen their bowels and clean them out. Of course, the mercury had a very detrimental effect on the men not the least of which was causing teeth to fall out of the gums and messing up the internal organs.

A modern explanation of Dr. Rush's pills that contained ~10 grains of calomel and ~10 to 15 grains of jalap, both potent laxatives that opened up the bowels,  Photo courtesy of The Disappearing Spoon on weebly.com.

So, what about my 1993 album question? Well, today Terlingua, with a permanent population of less than100, is a well-known tourist destination and serves as the drop off point for visitors to Big Bend National Park with last stop food, drink, and lodging. Terlingua also has that old hippie, country, lost in the desert, Devil may care, cold beer, and Willie Nelson vibe. Well, what better publicity for Terlingua than a 1973 funky rock and blues album by Jerry Jeff Walker entitled: VIVA TERLINGUA. The album included the giant hit, Up against the wall, the anthem of  south Texas (and many other beer halls).

He was born in Oklahoma
His wife's name's Betty Lou Thelma Liz
And he's not responsible for what he's doing
Cause his mother made him what he is

And it's up against the wall Redneck Mother
Mother, who has raised her son so well
He's thirty-four and drinking in a honky tonk
Just kicking hippies butts and raising hell

SILVER REEF: A STRIKE, A BOOM, THE BUST!

 Alternative Title: We’ll all be rich with the biggest silver strike this side of Hudson Bay.  Rudolph the Red-nosed reindeer (credit 1964 Videocraft International Ltd)

 

Saturday January 11, 2024. Hundreds of fishers are now crowding the back bays of the Mississippi River waiting for a sunnie or a fat perch, but most importantly the big ballgames are this weekend--The Packers and the Vikings, AKA the Pack and the Vikes, are in the NFL Payoffs. Most fishers will retreat to their tents or huts stocked with propane heaters, cold beer, chairs, color TVs, and lots of food. 

Nothing can beat the happiness of viewing a large amaryllis on a cold and cloudy January day.

I was spending the cold Wisconsin day, one only fit for ice fishers, in my cozy and warm office daydreaming while contemplating about the beautiful colors one can find in Christmas flowers. In between a snooze and a contemplation or two, I was examining some of my micro perky boxes and ran across an old box labeled BEAVERITE, WARREN LODE #5, MOHAVE CO AZ. Names like beaverite always pique my interest so I decided to explore the small sample and see what beaverite was all about! Little did I know that such exploration would lead down the proverbial rabbit hole with each side tunnel offering different confusing possibilities. For example, according to MinDat, beaverite is unknown from Warren Lode #5. More on that conundrum later. What I did find, however, was a fantastic paper by Biek and Rohrer (2006) describing the geology and mining history of a most interesting area in southwestern Utah, Silver Reef. For you see, Silver Reef in Beaver County, Utah, is the Type Locality for Beaverite, an uncommon lead iron copper sulfate: Pb(Fe³⁺₂Cu)(SO₄)₂(OH)₆.  So that serendipitous tidbit sent me sliding down the rabbit hole and finding, as Alice said—it’s rather curious you know, this sort of life.

Biek and Rohrer (2006) described the Silver Reef Mining Area as “a geologic anomaly, a historical curiosity, and an ecological novelty. It is one of the few places in the world where economic disseminated silver chloride [chlorargyrite: AgCl] was produced from sandstone."  I had the opportunity to visit Silver Reef during my late 1960s grad school days at the University of Utah, later in the 1980s while chasing fossils in southern Utah, and finally in spring 2023 during a two month, ”get out of cold weather” stint, in St. George, Utah. I tried very hard to locate a bit of the silver with each visit but no luck. Nada. However, there are many old mining structures, shafts, head frames, dump piles, equipment, a preserved original building, and a wonderful museum to keep one busy and enticed.

Stone walls remaining from a building at Silver Reef.

Some mine openings just head straight down.

Head Frame on Big Hill Reef. Photo from Reid and Rohrer, 2006.

 

Typical adit heading into the reef sandstone. Rebar gate is a recent addition to keep people out while allowing bats freedom in and out. Photo from Reid and Rohrer, 2006.

The Pine Valley Mountains form a beautiful backdrop at Silver Reef. These are some of the highest peaks in southern Utah (Signal Peak is 10,369 feet) and were formed from the Pine Valley Laccolith, perhaps the largest such igneous feature in the U.S. The quartz monzonite composing the laccolith has been dated as around 22 Ma.

Springdale Sandstone, AKA silver sandstone, exposed at Silver Reef. Public Domain Photo courtesy of arbyreed on Flicker.

The “silver history” of Silver Reef begin when a “vein of silver” was discovered in sandstone about 1866 by one John Kemple. However, poor ole John received a hearty round of laughs and guffaws since “everyone” knew silver veins occurred in “hard rocks”, usually igneous, and certainly silver was absent in most sedimentary rocks like sandstone. Ten years later a couple of Salt Lake City “bankers”, the Walker Brothers, decided to take a chance on the long-reported silver vein and sent a professional “claim guy” to stake several mining claims in the sandstone. Yep, you guessed it-----there really was disseminated silver chloride (AKA horn silver) in the sandstone and in three years over 2,000 miners were living and working on the original claims, as well as those migrating outward to dozens (hundreds) of new claims.  It turns out that not only was silver present at Silver Reef but also ores of lead, copper, and uranium. Google AI (accessed January 2025) stated, “the ore in the Silver Reef Mining District averaged 20 to 60 ounces of silver per ton.” According to MinDat (accessed January 2025) the Silver Reef District produced 7.52 million ounces of silver, 10.7 million pounds of copper, and an unknown amount of gold (probably not much). Most of this production happened during a five-year period of 1878-1882. By 1888 all the big mines had pulled up stake as the near surface ore was wiped out, the price of silver on the exchanges was heading toward the basement, and water was filling the lower tunnels. By 1903 the silver towns of Silver Reef were deserted. Sort of a typical western mining town history—a strike, the boom, and a bust!

But what about the story of silver in a sandstone? Biek and Rohrer (2006) described the Silver Reef area as one of the few places in the world where “economic disseminated silver chloride was produced from sandstone.”  A validation for ole John Kemple.

But where did the silver come from? What was the source? James and Newman (1986) suggested that “ground water leached metals from regional silver-rich rocks (presumably mostly from volcanic ash beds in the [Triassic] Chinle Formation) or from igneous systems and redeposited them in the [Jurassic] Springdale Sandstone, the first overlying permeable bed with organic material. The silver was probably transported by a sulfide-poor, chlorine-rich, brine and passed upward into anticlinal traps where it encountered reducing conditions or low-salinity groundwater that caused silver to precipitate.”

Biek and Rohrer, in their masterful 2006 article, noted that “although most workers familiar with the area agree that the Silver Reef deposits formed from metal-bearing low-temperature brines along permeable zones in the Springdale Sandstone, there is no consensus on the source of the metals, the chemistry and migration routes of ore fluids, and mechanisms to explain the variable distribution of silver, copper, and uranium.”  According to my 57-year-old class notes, that statement was about exactly what we learned in Lee Stokes’ stratigraphy classes at the University of Utah! Perhaps this is one of life’s persistent questions and I need to make a call to the Acme Building (Thanks Garrison Keilor)? You know: on the 12th Floor of the Acme Building, one man is still trying to find the answers to life’s persistent questions: Guy Noir, Private Eye.”

   Nostalgia is when you want things to stay the same!    Jeanna Moreau      

Interstate 70 bisects the San Rafael Swell and cuts through the tilted Jurassic Navajo Sandstone that is the Reef on the east side of the uplift.

In the Intermountain West one often sees the term “reef” with the most famous being the San Rafael Reef. In this usage reef does not refer to a nautical feature but to a resistant rock layer, usually indurated sandstone, that projects above its neighboring layers (often softer and easily erodible shale). At Silver Reef there are several large exposures of the resistant Springdale Sandstone (the silver bearing unit) that are exposed along, and on either side, of the nose of the Virgin Anticline, a small 30 mile long “buckle” in the rocks. The anticline is a compressional feature associated with the Lower Cretaceous Sevier Orogeny. These exposures are repeated in the rock stratigraphy due to numerous thrust faults moving the rocks around. The early silver miners thought that several different sandstone layers contained silver; however, the newly arriving geologists were able to map the faults and identify just a single silver-bearing sandstone. The resistant Springdale exposures at Silver Reef are known as the White, Buckeye, East, Big Hill, and Butte Reefs and are the major areas and mines of silver.

Notice how the reefs, outcrops of the Springdale Sandstone, are not connected but offset from each other giving the illusion that several different silver-bearing sandstone units were present. Photo from Biek and Rohrer (2006). The moral of the story—call a geologist if you locate silver!

 

Note the massive dump pile from a large mine in the reef.

Like the Phoenix, Silver Reef has experienced a rebirth, in fact, several periods of renaissance with the most successful mining activity being in 1950-1951 when 2500 pounds of uranium oxide, mostly carnotite, was hauled out for processing during the Colorado Plateau “uranium boom.” Visit Silver Reef today and you will notice a much larger rebirth as the old mines are now part of a large upscale home subdivision of Leeds and greater St George.

But wait, what about beaverite, the mineral that started this discussion? The Silver Reef beaverite, in current mineral classification, is known as beaverite-(Cu) due to copper as a major cation: Pb(Fe³⁺₂Cu)(SO₄)₂(OH)₆ and is the copper analogue of beaverite-(Zn) Pb(Fe³⁺₂Zn)(SO₄)₂(OH)₆  described from the Mikawa Mine in Japan.  It took me a long time to round up a copy of the original naming and description of the Silver Reef Type Specimen by Butler and Schaller in the 1911 American Journal of Science: check the QR code below created from https://rruff.info/Beaverite.

 

Butler and Schaller described the mineral: “Beaverite, a New Mineral. From the Horn Silver mine near the town of Frisco was collected a mineral that on examination in the laboratories of the United States Geological Survey proved to be a new species. For this mineral, which is a hydrous sulphate of copper, lead and ferric iron, the name Beaverite is proposed, after the name of the county from which it was first described. Occurrence.-The mineralization in the Horn Silver mine occurs along a fault plane that has thrown Tertiary lavas down against Cambrian-Ordovician limestone, the ore deposits being mainly a replacement of the volcanic rocks”.

 In 1992, Breidenstein and others redefined the chemistry and crystal structure of beaverite and suggested that beaverite-(Cu) is the most common of the related species with the zinc variety rare at only five different mines in Asia, Europe, and South America. In contrast, the Cu variety is uncommon but has a worldwide distribution; both are members of the Alunite Group > Alunite Supergroup.

A couple of general views of the beaverite-(Cu) specimen. FOV ~9 mm.

Note white--white cream mass, lemon yellow mass, The dark (Black) matrix is goethite. golden yellow mass, green exposures with some botryoidal, large quartz and salt and pepper scattered everywhere.

 

 

 

A golden yellow mass of submillimeter crystals of beaverite-(Cu). In fact,the mass in the middle photo is ~1 mm in width FOV. Essentially this is the limit of my photography skills.

 

Note the sub millimeter green balls of some copper mineral--malachite?, brochantite?, plumbojarosite (lead iron sulfate), osarizawaite?

Sub millimeter prismatic crystals of malachite?

MinDat noted that Beaverite-(Cu) has a yellow color that seems to range from a very pale yellow to a bright lemon yellow. However, as one peruses the photographs on MinDat and Google Photos it becomes apparent, at least to an ole plugger like me, that the mineral may also be noted in various shades of green and brown to golden brown to a golden yellow. Beaverite-(Cu) ranges from earthy masses without visible crystals (at least to me) to microcrystals often appearing as somewhat vitreous encrustations.  Whatever the case, the crystals are really tiny or almost non-visible, even with a decent, rockhound, binocular scope.

And what about the Warren Lode # 5? Not much I am afraid. Evidently it was a small claim for someone wishing for a polymetallic mine. Cannot locate any production figures. Mine not identified in Mineralogy of Arizona. No beaverite noted in MinDat; however, osarizawaite was identified (correctly?).              

To complicate identification, at least to ole plugger rockhounds, is a warning from MinDat: Beaverite-(Cu) Forms a solid solution series with its Al analogue osarizawaite .It can be distinguished from plumbojarosite  only by accurate determination of the Fe:Cu ratio. And, other Fe members of the alunite family are also visually very similar [to beaverite].  That, my fellow rockhounds is enough to scare most of us—unless we have access to nice electronic gizmos such as microprobes or XRDs!  

              

OK boys, let me tell you about the problem of identifying beaverite from the silver mines. Ole Mike just led us down a rabbit hole with that dang mineral!  Do we boot him out of the club or send him to catch the rabbit? ? Apologies to Cassius Marcellus Coolidge and his Public Domain photo.

Writing this paper was somewhat above my pay grade. One really needs an XRD or Microprobe to confirm visual identification of such small crystals. So don't quote any of my identifications as 100% accurate. As my hero Teddy Roosevelt said, Do what you can, with what you have, where you are.

 REFERENCES CITED

Bayless, P., U. Kolitsch, E.H. Nickel, and A. Pring, 2010, Alunite Supergroup: recommended nomenclature: Mineralogical Magazine, v. 74, no, 5.

Biek, Robert and C. Rohrer, 2006, Geology, mining history, and reclamation of the Silver Reef mining district, Washington County, Utah in R. Bon, R. Gloyn and G. Park (editors), Mining Districts of Utah: Utah Geological Association Publication 32.

James, L.P., and E.W. Newman,1986, Subsurface character of mineralization at Silver Reef, Utah, and a possible model for ore genesis, in Griffen, D.T., and W.R. Phillips, (editors), Thrusting and extensional structures and mineralization in the Beaver Dam Mountains, southwestern Utah: Utah Geological Association Publication 15.