OLD FRIENDS AND A RARE SULFOSALT: CYLINDRITE

Today, in the middle of Kansas, is a small town with a population of “around” 400 persons and maybe a hundred more if one counts free-range dogs.  I left the town ~55 years ago when the population was about 400 people plus the dogs.  It was a pretty "normal" farming community where a “typical farm” ranged from a section quarter to perhaps an entire section.  Larger acreages usually included some land rented by the farmer.  In addition, each farm usually raised a few head of livestock—hogs, cattle, chickens—for sale and for personal use.  Dogs abounded as did the free-range cats that were called “mousers.”  The cats were “just there” and were often quite wild.  In addition, because of inbreeding there were several of these animals that were not the sharpest pencil in the box!

 

Free-range dogs appreciate attention, especially after a long hike.  The broken clavicle?  Just a little friendly wrestling match!

I distinctly remember Saturday evenings when the outlying occupants came into to town for the weekly “trading” (as my mother called it) at the two grocery stores.  The trading was usually in the form of chicken eggs that a farmer might bring in and “trade” for a few groceries.  My father operated a gasoline (plus the usual small scale mechanic work) station and rarely took in trades unless he figured out that commodities would be his only way to collect a debt.  One time we had enough butter to last a year, and to a small kid that staple was magic compared to the terrible tasting oleomargarine that usually stocked our pantry.

One of the great things about growing up in such a small town was the fact that kids were like the local dogs---free-range. We simply wandered all over town and had a boundary of about one mile in any rural direction to explore.  Just be home by supper.

 

Old friends after a tough day of hunting for turdites.  That Kansas sun can be hot so don't laugh at the hat!

I bring this up since I was a rockhound at an early age and always picked up and hauled home anything that caught my eye.  But, I also named many of these special rocks—nothing serious since I didn’t have the slightest idea what they really were.  Therefore, my names were like crickite (we pronounced the streams cricks) for finding the stone in a creek, roundyites (shape), slaberoos due to the layering, and turdites, a young boy’s favorite rock name (giggle, giggle), etc.  The names I conjured up generally were due to either shape or location.  Today, I suppose most new mineral names come from honoring a person.  However, one mineral I could have named as a child is the sulfosalt cylindrite (FePb₃Sn₄Sb₂S₁₄).  What appears as crystals in cylindrite specimens are actually rolled up flat sheets in the form of a cylinder, kind of like rolled tobacco leaves in a cigar.  Unfortunately, I never had a chance to collect the mineral as most specimens come from Bolivia.

 

Massive cylindrite mixed with the typical rolled-up sheets.  Longest cylinder in center is ~1.1 cm.

 

Photomicrograph (black & white) of above specimen.  The shiny metallic luster does not work well with my scope. Again, the longest cylinder is ~1.1 cm.

Cylindrite belongs to the sulfosalt minerals, a member of the sulfides group.  Sulfosalts contain a metal (mostly lead, copper, iron or silver although a few others, mercury, zinc, vanadium may be present), a semi-metal like arsenic, germanium, bismuth, antimony, or the metals tin or vanadium, and then sulfur (Richards, 1999).  

Because of the interesting habit of cylindrite, I found a specimen last February at one of the Tucson dealers (Shannon and Sons Minerals). The mineral is black to dark gray in color with a metallic luster.  It is quite soft at ~2.5 (Mohs) and has the traditional opaque diaphaneity of metals and the malleable tenacity. Although cylindrite appears in massive or cylindrical forms, Triclinic crystals are present but tiny (beyond the limits of my microscope).  I really don’t understand the mechanism behind the formation of cylinders.  Evidently, cylindrite originally occurs as stacked and layered structures but these flat sheets begin to deform from pressure and “roll up” into smooth cylinders.  MinDat states that “layer curving is one of the ways of an accommodation of the dimensional sheet misfit by a cylindrite crystal.”  That is about all that I can understand!  However, I do note that several references refer to cylindrite rolls as crystals; however, the large rolls are not individual crystals but rolled up sheets and the sheets are composed of individual crystals.

Cylindrite is a fairly rare mineral and most specimens come from mines in Brazil; my specimen was collected from the Itos Mine, Oruro City.  There are several tin-silver mines in the area and some produce cylindrite.  The mineral seems to form as the result of hydrothermal solution next to an igneous intrusion. For reasons beyond my comprehension, there are numerous studies that have been completed on synthesizing cylindrite and relatives (mainly franckeite).  During these studies microprobe analyses indicate there may be some solid solution series between lead and tin in cylindrite. I have read a number of these papers without really understanding much—see Jiuling and others, 1988.  I simply picked up my specimen due to the nifty habit of rolled up cylinders.

OLD FRIENDS

Can you imagine us years from today,
Sharing a parkbench quietly
How terribly strange to be seventy

Old friends, memory brushes the same years,
Silently sharing the same fears.

                             Simon and Garfunkel  

REFERENCES CITED

Jiuling, L., H. Jiashan, Z. Kezi and Z. Guilan, 1988,  An experimental study on three quaternary phases in the Fe-Sn-Sb-S System: Pb-free Franckeite, Pb-free Cylindrite and (Fe, Sb)-Ottemannite s.s.: Acta Geologica Sinica, v. 1, no. 4.

Richards, J.P., 1999, Encyclopedia of Geochemistry in Encyclopedia of Earth Sciences Series, C.P Marshall and R.W. Fairbridge, eds.: Springer Netherlands.   

IMPORTING GEMS, IVORY, AND CORAL; QUESTIONS, I GET QUESTIONS!

This posting is a little off the track of my "normal" work; however, it might be of interest to some readers!  As a member of the Colorado Springs Mineralogical Society, I also am a member of the Rocky Mountain Federation of Mineralogical Societies (see www.rmfms.org).  The Federation has a number of Committees (see website) and I chair the International Relations Committee---not because I have a great deal of knowledge about such matters but because I volunteered to help the Federation.  In fact, the recent posting on BLM fossil collecting rules was written for another Committee I chair, the Public Lands Access Committee.  The following is my report for the annual Federation meeting---March, Albuquerque.    

RMFMS INTERNATIONAL RELATIONS COMMITTEE

Mike Nelson                   

csrockguy@yahoo.com  www.csmsgeologypost.blogspot.com

I have found that being Chair of the RMFMS International Relations Committee is not an onerous job and actually produces some interesting questions.  Some are easily answered, while others require some serious thought before an answer.  Most questions coming from international rockhounds fall in the area of  “I am visiting INSERT STATE where can I collect minerals or fossils?”  I make an attempt to answer these inquiries for states of which I am somewhat familiar—most of the Great Plains, a few in the Midwest and Rocky Mountains.  My first line of defense is to suggest state rockhounding and geology “travel” books, the second is to recommend websites of the various state geological surveys. My third line is to suggest joining a local rock and mineral club in order to participate in their fields trips and will point rockhounds to appropriate clubs. Then I attempt to explain about collecting on federal and state land as well as trespassing on private land.  Collecting minerals would seem an easy talk; however, try explaining claims and markers—and my warning about: do not even venture to Mt. Antero looking for aquamarines.  First, because of the high altitude (13,000 feet) a rockhound could die, but second, virtually the entire mountain is claimed.

Explaining about collecting fossils used to be an easy task---stay away from vertebrate fossils, fill up any collecting holes in searching for invertebrate fossils, and keep under the pound limit for petrified word.  However, the new collecting rules on USFS and BLM lands confuses even professional paleontologists.  

I have received three inquiries from international rockhounds with questions like “I purchased this specimen (photo enclosed) at a mineral fair but the only listed locality is INSERT STATE.  Can you help me find the locality?”  A photo of calcite sand crystals was fairly easy to pinpoint as Rattlesnake Butte in South Dakota (some want latitude and longitude).  I gave an educated guess for azurite blueberries as coming from the Blue Crystal Mine in the La Sal Mountains in Utah.  A specimen with garnets probably came from New England but where?

I also receive requests to send or trade minerals.  One person wanted me to send over samples of sand, including a sample containing azurite crystals.  I have not provided any sample or minerals for international shipments since some countries have laws prohibiting the import of rockhounding “stuff.”

A couple of gentlemen from the U.S. wanted information about bringing precious stones back from their upcoming vacation visit to southeast Asia.  What do I know about that—very little.  First, I suggested contacting a reputable dealer and not purchasing any nice-looking stones (like rubies) from a street seller.  Second, I told them to search information established by U.S. Customs and Border Protection.  For satisfying my own curiosity I found the following information:

Personal imports of these items are usually cleared informally and do not require a Customs bond. However, if you purchased them while you were abroad, ensure you declare them when clearing Customs and Border Protection (CBP) on the CBP Form 6059B. Imports of diamonds, pearls, rubies, sapphires and emeralds from countries with normal trade relation status are duty-free as long as they are not permanently strung, set or mounted. Additional duty rates for these items can be found in the Harmonized Tariff Schedule (HTS) in chapter 71.  

When these items are set, or mounted with some sort of metal, they are classified as jewelry and subject to duty. These rates can also be found in chapter 71. Diamonds also require a Kimberley Certificate, more information can be found on the State Department brochure and website. 

Please be aware that there are sanctions against diamonds imported from Sierra Leone, Angola, Liberia and other countries. Visit the Kimberley Process website for the most recent list of countries.  See the Kimberley Process Certificate Scheme.  Additional information on sanctions against diamonds from these countries can be found Office of Foreign Assets Control's Web site.  Additional information can also be obtained from the World Diamond Council.

Finally, a person wanted to know about buying ivory for his scrimshaw work and “coral” for jewelry.  He/she also wanted to know about using “fossil ivory” (Mammoth and Mastodons and relatives).

There has been a ban on ivory (elephant) importation since the late 1980s.  The U.S. Fish and Wildlife Service also notes the following are prohibited---see: https://www.fws.gov/le/travelers.html);

• All products made from sea turtles
• All ivory, both Asian and African elephant
• Rhinoceros horn and horn products
• Furs from spotted cats
• Furs and ivory from marine mammals
• Feathers and feather products from wild birds
• Most crocodile and caiman leather
• Most coral, whether in chunks or in jewelry

In other words, Fish and Wildlife states: The United States generally prohibits the importation of ivory. Don’t bring home raw ivory or ivory jewelry, carvings, or figurines made from the tusks of either African or Asian elephants. Avoid raw or carved ivory from the teeth or tusks of walruses, whales, narwhals, and seals. 

A couple of decades ago I presented a paper on muskoxen at a University in Saskatoon.  While waiting in the airport I wandered through the gift shop and noted these “cute” little furry seal skin dolls.  I almost purchased one as they were popular among travelers.  A stroke of genius: the cute little dolls were confiscated by U.S. federal agents after entering the country (see list above).

There are also a host of regulations and questions revolving around selling and trading “antique” ivory chess sets, figurines, pianos, etc. that are personal items found in the home.  Answering questions about this sort of trade is beyond my pay grade so contact federal authorities.  With that noted, before you hide grandpa’s watch fob, realize that: federal wildlife laws and regulations such as CITES, the ESA, and the AfECA do not prohibit possessing or display of ivory, provided it was lawfully acquired. There is no certification requirement or process to register ivory items and you do not need a permit from the Service to possess or display ivory for noncommercial purposes. We (U.S. Fish and Wildlife Service) recommend that you maintain any records or documentation you have that demonstrates the origin and chain of ownership of the item. We recommend that you provide all documentation to any future recipient of your elephant ivory item. Check to make sure that you are also in compliance with local and state laws. Contact the state to check on their requirements.

But what about using Mammoth or Mastodon ivory?  I do note that “fossil ivory” is common at most rock and mineral shows; therefore, the trade must be legal.   Maybe, but then again, some states are starting to prohibit the sale/purchase of ivory from Mammoths (usually) or Mastodons.  According to the American Association of Paleontological Suppliers (AAPS), California, New Jersey, Hawaii, and New York have new laws banning the sale of “fossil ivory.”  For example, the Hawaii law states: (d) Except as authorized under section 183D-6, no person shall sell, offer to sell, purchase, trade, or barter for any part or product from mammoth (Mammuthus), although the species is extinct.

AAPS also notes (www.aaps-journal.org) that several other states are examining/constructing laws concerning the sale of “fossil ivory” ----

1. New Arizona; House Bill HB 2176 (Includes Mammoth Ivory and teeth), Introduced January 25, 2016, Died in Committee
2. Arkansas; Senate Bill 928 (Killed in Committee)
3. California; Assembly Bill No. 96 (Includes Mammoth Ivory), Passed the State Senate September 2, 2015, Passed the State Assembly September 4, 2015, Sent to the Governor for his signature. This act shall become operative on July 1, 2016
4. Connecticut; Proposed Bill No. 5700 (Vague definition of Ivory), Tabled for the Calendar, House May 5, 2015.
5. Florida; Senate Bill 1120 (Includes Mammoth Ivory), Died in Environmental Preservation and Conservation Location: In committee/council (EP), May 1, 2015.
6. Hawaii; Senate Bill 674 (Includes Mammoth Ivory), Currently in Committee, scheduled to become Effective 01/01/16. 7. Illinois; Senate Bill 1858 (Includes Mammoth Ivory), Currently in Committee, May 15, 2015.
8. Iowa; SF 30 (Includes Mammoth Ivory) In Sub-committee February 11, 2015.
9. Maryland; House Bill 713 (Vague definition of Ivory), Unfavorable Report by Judiciary, remains in Committee, March 16, 2015.

10. Massachusetts; House 1275 (Includes Mammoth Ivory) Remains in Committee January 20, 2015.
11. Nevada; Senate Bill 398 (Includes Mammoth Ivory) Remains in Committee, Pursuant to Joint Standing Rule No. 14.3.1, no further action allowed April 11, 2015.
12. Oklahoma; HB1787 (Vague definition of Ivory), Second Reading referred to Wildlife Committee February 3, 2015.
13. Rhode Island; House 5660 (Includes Mammoth Ivory) Committee recommended measure be held for further study, April 15, 2015.
14. Vermont; House 297 (Includes Mammoth Ivory), In Committee February 24, 2015; in Conference Committee 2016.

15. Washington; House Bill 1131 (Includes Mammoth Ivory) By resolution, reintroduced and retained in present status. June 28,2015.
16. Oregon; Senate Bill 913 (Includes Mammoth Ivory). Currently in Committee.

17. Delaware; Senate Bill 156 (Includes Mammoth Ivory) Senate Banking and Business Committee June 24, 2015.
18. Michigan; Senate Bill 371 (Includes Mammoth Ivory); in Committee.
19. Virginia; Senate Bill 1215 (Killed in Committee).

If I thought regulations concerning ivory were difficult to understand, I certainly was not prepared for “corals.”   The only thing I know about bringing dried pieces of coral into the U.S. came from an experience several years ago, (~10) when Fish and Wildlife (or some federal agency) removed small pieces of dried coral from my backpack as I was returning from a visit to the Caribbean.  “They” left behind a card stating that such items were not permitted into the U.S.  What I have now found from Fish and Wildlife is:  Coral species may be protected under international, domestic or even state environmental laws.  Black corals (Antipatharia) were listed in Appendix II of the Convention on International Trade in Endangered Species of Wild Fauna and Flora in 1981.  In 1985, amidst concerns about the effects of commercial trade on fragile coral ecosystems, the CITES Parties listed all stony corals, blue corals (Helioporidae), organ pipe corals (Tubiporidae), and fire corals (Milleporidae)…  Lace corals (Stylasteridae) were later added… and China has listed 4 species of red coral…

Some coral species are listed under the Endangered Species Act. Visit the U.S. Fish & Wildlife Service's (Service) Endangered Species Program page to learn more about these listings.

Each U.S. state may have separate regulations that control the harvest of coral within its waters. In addition, there are different regulations when handling wild-harvested or captive-bred coral. It is strongly recommended that you contact your state wildlife agency and the Service's Branch of Permits before importing or exporting coral.

What that all means is that I don’t have the slightest idea if you can bring coral into the U.S. for making jewelry!  Contact Fish and Wildlife.

As a bit of small trivia, do not try and bring the liquor Absinthe (anything containing Artemisia absinthium) into the U.S.  The only thing I know about the liquor is that cool guys and ladies drink the bitters in New Orleans.

The U.S. Customs and Border Protection (CBP) enforces federal regulations on absinthe brought into the country. So, recognize their rules and realize your bottle may be seized if:

• The absinthe is not "thujone-free."  Thujone is a chemical compound found in wormwood that acts on certain receptors in the brain.  I suppose the thujone-free stipulation is similar to some medicinal marijuana that has a very low content of tetrahydrocannabinol (THC), the psychoactive part of cannabis.  But that is only a guess.   
• The bottle has "absinthe" as the brand name
• The bottle has "artwork and/or graphics" that depicts "images of hallucinogenic, psychotropic or mind-altering effects."

Remembering my days as a Ranger leading field trips in the Uinta Basin, I note Artemisia species include A. vulgaris (common mugwort), A. tridentata (big sagebrush), A. annua (sagewort), A. absinthium (wormwood), A. dracunculus (tarragon), and A. abrotanum (southernwood).  I never tried to distill the abundant sagebrush!

Life-long learning needs to be fun and interesting!

BLUE SAMPLEITE: COPPER PHOSPHATE

It is not knowledge, but the act of learning, not possession but the act of getting there, which grants the greatest enjoyment. 

          Carl Friedrich Gauss

One of the interesting aspects of collecting minerals is trying to find two minerals where radicals (an atom or molecule [usually the case in mineralogy] with an odd number of electrons) are able to substitute for each other in the chemical formula and create new species.  Radicals are highly reactive since they are always looking around for something to bond with (not unlike many high school boys I knew) since they have a free electron wandering around in orbit.  This free wanderer wants to meet up with an atom looking to obtain an electron in order to stabilize.

Three of the more interesting radicals are PO₄, VO₄, and AsO₄ (phosphorus, vanadium and arsenic combined with oxygen) and are usually organized as the Phosphate Class.  All radicals operate as anions and have a negative charge of -3.  Therefore, they easily (I think) combine with metallic cations with a positive charge.  The resulting minerals are termed the Phosphates, Vanadates, and the Arsenates and all are important in the mineral world.  For example, the mineral apatite (with its many descriptive terms) is the backbone of vertebrate teeth and bones.  In addition, vanadinite with the red barrel-shaped crystals, and all of the colorful arsenates (like the pink erythrite), are eagerly sought by mineral collectors. 

  

The arsenate, phosphate and vanadate radicals are of similar size and Jones (2011) noted that solid solution series commonly exist between these radicals with both end members and intermediate members between the arsenate and vanadate radicals and the phosphate and arsenate radicals.  There are no intermediate members between the vanadate and phosphate end members.  This is an interesting situation since in most solid solution series the substitutions are made by the positively charged cations.

At the 2016 Tucson show I was able to pick up a nice arsenate, lavendulan [NaCaCu₅(AsO₄)₄Cl-5H₂O], a hydrated copper arsenate that forms as a secondary mineral in “oxidized zones of some copper deposits” (MinDat). The specimen appears as sort of a crust of intense electric blue on the matrix.  However, on closer examination under high power one can observe the crust is composed of very tiny aggregates of thin platy crystals, some of which form rosettes. An older label indicates collection at El Guanaco Mine, Santa Catalina, Antofagasta Province, Chile, where MinDat noted 31 valid minerals and two type localities.  At the mine copper and gold veins are emplaced in Upper Cretaceous and Paleocene volcanic sequences.  I presume, but am uncertain, that both the copper and the arsenic could be the result of oxidation of the primary mineral enargite [Cu₃AsS₄].

I also have in my collection a small sample of sampleite (a hydrated copper phosphate) that was picked up at the Denver Show.  Now this particular mineral is the phosphate analogue of lavendulan—note the phosphate radical: NaCaCu₅(PO₄)₄Cl-5H₂O.  As noted above, the similar size of the radicals allows substitution of the phosphate radical for the arsenate radical. 

Sampleite is blue to blue-green in color and is found in a variety of habits from encrusting to rectangular tabular crystals to rosettes.  It has a hardness ~4.0 (Mohs), is transparent with a light blue streak and has a pearly luster.  Sampleite is a fairly rare mineral, compared to lavendulan, but both occur in the oxidized zones of arid-region copper deposits.

 

Small cluster of sampleite crystals, and "balls (upper blobs).  Total width of cluster is ~1 mm. 

Cluster of small blades of sampleite.  Width of large cluster ~1.5 mm.

Cluster of nondescript sampleite crystals.  Width of cluster ~.5 mm.

My small mineral specimen came from the dumps associated with the Endeavour 26 Mine in New South Wales, Australia. MinDat notes that Endeavor 26 is both a surface and underground (currently) gold-copper complex developed as a porphyry vein mineralization in a monzonite that is part of the Goonumbla volcanic complex (Ordovician). The major primary (hypogene) minerals are bornite, chalcopyrite and pyrite.  However, the most interesting thing about the mine is the presence of two distinct and major oxidation zones, one of Carboniferous age and one of Cenozoic; therefore, the host rocks have experienced prolonged weathering cycles (O'Sullivan and others, 2000). 

The upper oxidized zone is dominated by the secondary copper phosphate minerals libethenite (Cu₂PO₄OH), pseudomalachite (Cu₅(PO₄)₂(OH)₄) and the uncommon sampleite. However, this secondary phosphate mineralization was preceded by the formation of another secondary mineral, atacamite (Cu₂Cl(OH)₃).   Beneath the phosphates is a zone dominated by malachite (Cu₂CO₃(OH)₂), azurite (Cu₃(CO₃)₂(OH)₂) and chrysocolla (CuSiO_3--nH₂O) that gives way at depth to a thin native copper-cuprite (Cu₂O)-chalcocite (Cu₂S) supergene enriched zone (Clissold and others, 2005).

So, the answers I needed to locate were to the questions about: 1) the original source of the phosphorous; and 2) why are the secondary phosphate minerals located in the upper zone only?  Crane and others (2000) found that weathering of apatite group minerals, especially hydroxylapatite, provided the phosphate for the PO₄ radical.  In addition, the zoning of the copper phosphate minerals is due to the distribution of the apatite minerals in the host rock and the intensity of weathering (Ollier, 1984).  Ain’t  learning fun?

For descriptions of pseudomalachite and libethenite (January 4, 2016), lavendulan (March 21, 2016), and atacamite (October 9, 2014) see Blog postings.

REFERENCES CITED

Crane, M.J., J.L. Sharpe, and P.A. Williams, 2001, Formation of chrysocolla and secondary copper phosphates in the highly weathered supergene zones of some Australian deposits: Records of the Australian Museum, v. 53.

Clissold, M.E., P. Leverett, and P.A. Williams, 2005, Chemical mineralogy of the oxidized zones of the E22, E26 and E27 ore bodies at Northparkes, New South Wales in Roach, I.C., ed., 2005, Regolith 2005-Ten Years of CRC LEME.

Ollier, C., 1984. Weathering: Longmans Publishing Group, London.

O’Sullivan, P.B., D.L. Gibson, D.L Kohn, B. Pillans, and C.F. Pain,  2000, Long-term landscape evolution of the Northparkes region of the Lachlan Fold Belt, Australia: constraints from fission track and paleomagnetic data: Journal of Geology 108.