The Fascinating World of Biominerals

1. The Fascinating World of Biominerals George R. Rossman Division of Geological and Planetary Sciences California Institute of Technology Pasadena, CA www.pulso.com/secot/32.htm

2. Fossil Biominerals Fossil mineralized hard parts of organisms are first preserved from multicellular life forms that lived about 540 million years ago. Multicellular life itself evolved more than 3000 million years ago. Wim van Egmond Miocene Foram test

3. Apatite Group Apatite: Ca5(PO4)3(OH) Fluorapatite: Ca5(PO4)3F Carbonate apatite Ca5(PO4,CO3)3(OH,O) Durango, Mexico

4. Calcium Carbonate Phases Pseudomorph of calcite after ikaite, Russia. On display at the Carnegie museum, Pittsburgh. Carnegie Museum

5. Calcium Carbonate Biominerals • Organisms use calcite, aragonite, vaterite, monohydrocalcite and amorphous hydrous calcium carbonate. • In the Kingdom Monera (archaebacteria, blue-green algae) calcite, aragonite and monohydrocalcite are used. • In the Kingdom Protoctista (sea-weeds, • slime molds) calcite, aragonite, vaterite • and amorphous calcium carbonate is used. • In the Animal Kingdom, all four are used. • In the Plant Kingdom, calcite, aragonite and vaterite are used. Photo Credit: The Potteries Museum

6. Brittle Star’s calcite optics Alzenberg et al. (2001) Brittle stars have the ability to rapidly change color. Each calcite lens directs light to a nerve fiber.

7. Tribolite’s Calcite Eyes www.ucmp.berkeley.edu/collections/invert.html from Clarkson 1975 Paleoplace.com

8. Aragonite www.ammonite.com Sr, Mg, and organics in water can favor aragonite formation. Black Bearpaw Shales, Alberta Aragon, Spain Erzberg, Striermark, Austria

9. Vaterite, CaCO3 Microbial biscuits in Lake Issyk-Kul, Kyrgyzstan. A layer that often occurs on (parts of) cormorant’s eggs. Sagittal otoliths with vaterite replacement in lake trout in the Great Lakes. Spicules of topical ascidians (sea squirts). Vaterite spicules Parmentier J & van Egmond W (1998) http://micscape.simplenet.com/mag/artaug98/tuni2.html Vaterite cluster Spangler, G (1995) http://www.fw. umn. edu/biochr/ GRS_home/FRD_ page/FRD.html Aragonite otoliths Scott C: www.keele.ac.uk/depts/ch/groups/csg/cas/

10. Pomacea paludosa (Apple Snail) Aragonite shell Vaterite egg capsules Harry G. Lee Pomacea paludosa - Lake Oklawaha, FL Amorphous CaCO3 in the foot.

11. Monohydrocalcite Crusts on the walls of caves where cold, Mg-rich waters drip. Lake Issyk-kul, Kyrgyzstan; A saline lake. A precipitation from halophilic strains of Bacillus that live in saline soil. A guinea pig bladder stone. Lake Issyk-Kul’ and Tien Shan, Kyrgyzstan http://earth.jsc.nasa.gov/

12. Ikaite Ikaite, CaCO3 · 6H2O, was discovered in Greenland in a fjord at the site of a carbonate-rich near-freezing water seepage where it forms tall underwater columns. When it warms to room temperature, it decomposes into a mush of water and anhydrous CaCO3 . Images from: Seaman P and Buchardt B (1998) http://www.geocities.com/RainForest/Vines/1486/

13. Silica Amorphous silica is used by a wide variety of organisms. These include foraminifera, radiolarians, heliozoata, bachillariophyta, sponges, annelids, molluscs, arthropods, echinoderms and plants @ University of Sydney Radiolarian Museum of Paleontology Hamline University Sponge spicule Foram test

14. Bamboo Silica A silica residue is left when the organic matter in a bamboo leaf is dissolved in sodium hypochlorite (bleach).

15. Bamboo Silica

16. Bamboo Silica

17. “Bamboo contains silica (sand)and dulls blades quickly.” Bamboo silica

18. Silica structures in a sponge

19. Monera Forams Fungi Sponges Annelids Mollucs Arthropods Chordates Iron oxides Magnetite Fe3O4 x x x x Maghemite g-Fe2O3 ? Goethite a-FeO(OH) x Lepidocrocite g-FeO(OH) x x ‘Ferrihydrite’ x x x x x Amorphous hydrous iron oxides x x x

20. Nip Island, Palau

21. Chitons (cl. Polyplacophora) eating rock) Eating Rock

22. Scrape Marks in the carbonate

23. Chitons library.thinkquest.org/J001418/chiton.html www.vattenkikaren.gu.se/fakta/arter/mollusca/prosobra/helcpell/helcpee.html http://edweb.sdsu.edu/triton/tidepoolunit/Graphics/jpgs/OwlLimp.jpg

24. Chiton Radula

25. Chiton Teeth Cryptochiton stelleri

26. Chiton’s and snail’s teeth Magnetite Lepidocrocite Amorphous Some molluscs use amorphous silica www.microscopy-uk.org.uk/mag/artsep01/rhsnail.html Snail radula (Genus Katharina)

27. Magnetite crystals produced by magnetotactic bacteria

28. Goethite sheaths around Leptothrix bacteria The sheathed bacteria are common in aquatic habitats www.bsi.vt.edu/chagedor/biol_4684/Microbes/Leptothrix.html

29. Bacterially precipitated MnO2 Manganese oxide precipitates around spores of the marine bacillus, SG-1, isolated from sediments off Southern California. It is a sheet oxide, probably birnessite

30. Polymorphs of MnO2 Pyrolusite 1 x 1 Ramsdellite 1 x2 Hollandite 2 x 2 Romanechite 3x 2 Todorokite 3 x 3 Birnessite sheet

31. Iron Sulfides Pyrite is used by Monera (archaebacteria, blue-green algae)

32. Fluorite mysid statolith Opossum Shrimps www.museum.vic.gov.au/crust/mysidgal.html Statoliths are small grains that help the animal keep orientation.

33. Molpadia A holothurian (sea cucumber) Holothurians are echinoderms that have a calcareous exoskeleton. It has a leathery consistency. The exoskeleton of Molpadia contains biominerals.

34. Molpadia calcium phosphate skin granules Sea cucumber These granules are rigorously X-ray amorphous. When heated, they show lines from hematite and carbonate apatite, Ca5(PO4,CO3)3(OH,O).

35. Molpadia calcium iron phosphate skin granule

36. Molpadia calcite spicule These are found in early postlarval individuals.They are replaced by the amorphous calcium-iron phosphate in the adult stage. Molpadia intermedia

37. Juvenile Molpadia calcite anchor spicule

38. Ascidians The ascidians are are a class of tunicates. They are also called sea squirts. Tunicates have a tunic that protects them from predators. Their tunics contain biominerals. Ascidian species collected in the vicinity of Asamushi Marine Biological Station.

39. Aragonite spicules from an ascidian Halocynthia roretzi is a popular sea food in Japan home.hiroshima-u.ac.jp/akirahs/eng/ascidian.html

40. Herdmania (ascidian) vaterite

41. Culeolus (ascidian) amorphous CaPO4

42. Sulphates: Celestite, SrSO4 Barite, BaSO4Gypsum, CaSO4 Celestite is used by marine protoctists (algae & diatoms) to form skeletons. Because sea water is undersaturated in SrSO4, it dissolves rapidly when the organism dies. Gypsum is used by Coelenterata Barite is used by Rhizopodea (protozoans) and Charophyta (green algae)

43. Nontronite Na0.3 Fe23+ (Si,Al)4 O10 (OH)2 · nH2O A low aluminum, nearly monomineralic greenish nontronite with a sheath morphology is found in the vicinity of white smokers. Fe-oxidizing bacteria play a role in its formation. Kohler B, Singer A, Stoffers P (1994) Biogenic nontronite from marine white smoker chimneys. Clays & Clay Minerals 42:689-701 White smoker is the name for chimneys made out of iron, sulfur, lead, and zinc sulfide minerals that have high temperature (250-300°C) plumes of white "smoke" coming out of them. Much of the white smoke is caused by crystallization of very fine-grained minerals made out of anhydrite (CaSO4). Bruce Strickrott, DSV Alvin Pilot. www.lostcity.washington.edu home.t-online.de/home/g.m.e.b.schuster/_nontro.jpg www.ocean.udel.edu/deepsea/

44. Human Biomineralogy Structural components: Teeth, Bones: apatite group minerals Pathology: oxalates, phosphates carbonates Sensorary: Fe-oxide?

45. Calcium oxalate dihydrate (weddellite) These crystals of CaC2O4 · 2H2O were recovered from a human thyroid gland

46. Calcium oxalate monohydrate (whewellite) CaC2O4 · H2O These crystals formed in the myocardium of an 48-year old alcoholic woman.

47. Kidney Stones Other biominerals: Whitlockite Struvite Brushite Carbonate-apatite Newberyite Calcite Weddellite www.radsci.ucla.edu Calcium oxalate monohydrate (whewellite) www.herringlab.com

48. Summary In 1962, Caltech paleoecologist Heinz Lowenstam discovered that organisms produce iron minerals. Today, biomineralogy is a rapidly growing field. More than 60 different inorganic crystals are recognized as products of life. Three billion years of microbial action led to the accumulation of many valuable ore deposits.