The Fascinating World of Biominerals www pulso comsecot32

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

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 Fossil Biominerals Miocene Foram test

Apatite Group Apatite: Ca 5(PO 4)3(OH) Fluorapatite: Ca 5(PO 4)3 F Carbonate apatite Ca 5(PO 4, CO 3)3(OH, O) Durango, Mexico

Calcium Carbonate Phases Phase Formula Structure Calcite Ca. CO 3 Trigonal Aragonite Ca. CO 3 Orthorhombic High Mg/Ca ratio Vaterite Ca. CO 3 Hexagonal higher T Monohydrocalcite Ca. CO 3·H 2 O Hexagonal low T Ikaite Ca. CO 3· 6 H 2 O Monoclinic Carnegie Museum Comments forms near 0°C Pseudomorph of calcite after ikaite, Russia. On display at the Carnegie museum, Pittsburgh.

Calcium Carbonate Biominerals Organisms use calcite, aragonite, vaterite, monohydrocalcite and amorphous hydrous calcium carbonate. In the Animal Kingdom, all four are used. In the Plant Kingdom, calcite, aragonite and vaterite are used. Photo Credit: The Potteries Museum 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.

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.

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

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

Vaterite, Ca. CO 3 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). Parmentier J & van Egmond W (1998) http: //micscape. simpl enet. com/mag/artaug 98/tuni 2. html Vaterite spicules 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/

Pomacea paludosa (Apple Snail) Vaterite egg capsules Harry G. Lee Aragonite shell Pomacea paludosa - Lake Oklawaha, FL Amorphous Ca. CO 3 in the foot.

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/

Ikaite, Ca. CO 3 · 6 H 2 O, 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 Ca. CO 3. Images from: Seaman P and Buchardt B (1998) http: //www. geocities. com/Rain. Forest/Vines/1486/

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

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

Bamboo Silica

Bamboo Silica

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

Silica structures in a sponge

Monera Forams Fungi Sponges Annelids Mollucs Arthropods Chordates Iron oxides Magnetite Fe 3 O 4 x x x Maghemite g-Fe 2 O 3 ? Goethite a-Fe. O(OH) x Lepidocrocite g-Fe. O(OH) x x ‘Ferrihydrite’ x x x x Amorphous hydrous iron oxides x

Nip Island, Palau

Chitons (cl. Polyplacophora) eating rock) Eating Rock

Scrape Marks in the carbonate

Chitons library. thinkquest. org/J 001418/chiton. html www. vattenkikaren. gu. se/fakta/arter/mollusca/prosobra/helc pell/helcpee. html http: //edweb. sdsu. edu/triton/tidepoolunit/Graphics/jpgs/Owl. Limp. jpg

Chiton Radula

Cryptochiton stelleri Chiton Teeth

Chiton’s and snail’s teeth Magnetite Lepidocrocite Amorphous Some molluscs use amorphous silica www. microscopy-uk. org. uk/mag/artsep 01/rhsnail. html Snail radula (Genus Katharina)

Magnetite crystals produced by magnetotactic bacteria

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

Bacterially precipitated Mn. O 2 Manganese oxide precipitates around spores of the marine bacillus, SG-1, isolated from sediments off Southern California. It is a sheet oxide, probably birnessite

Polymorphs of Mn. O 2 Pyrolusite 1 x 1 Ramsdellite 1 x 2 Hollandite 2 x 2 Romanechite 3 x 2 Todorokite 3 x 3 Birnessite sheet

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

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

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

Molpadia calcium phosphate skin granules Sea cucumber These granules are rigorously X-ray amorphous. When heated, they show lines from hematite and carbonate apatite, Ca 5(PO 4, CO 3)3(OH, O).

Molpadia calcium iron phosphate skin granule

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

Juvenile Molpadia calcite anchor spicule

Ascidians The ascidians 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.

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

Herdmania (ascidian) vaterite

Culeolus (ascidian) amorphous Ca. PO 4

Sulphates: Celestite, Sr. SO 4 Barite, Ba. SO 4 Gypsum, Ca. SO 4 Celestite is used by marine protoctists (algae & diatoms) to form skeletons. Because sea water is undersaturated in Sr. SO 4, it dissolves rapidly when the organism dies. Gypsum is used by Coelenterata Barite is used by Rhizopodea (protozoans) and Charophyta (green algae)

Nontronite Na 0. 3 Fe 23+ (Si, Al)4 O 10 (OH)2 · n. H 2 O 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. home. t-online. de/home/g. m. e. b. schuster/_nontro. jpg 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 (250300°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 (Ca. SO 4). Bruce Strickrott, DSV Alvin Pilot. www. lostcity. washington. edu www. ocean. udel. edu/deepsea/

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

Calcium oxalate dihydrate (weddellite) These crystals of Ca. C 2 O 4 · 2 H 2 O were recovered from a human thyroid gland

Calcium oxalate monohydrate Ca. C 2 O 4 · H 2 O These crystals formed in the myocardium of an 48 -year old alcoholic woman. (whewellite)

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

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.