LITHIUM OCCURENCE

Lithium does not occur freely in the nature, but is found combined in small amounts in nearly all igneous rocks, in the waters of the many mineral springs and in seawater. Identified lithium land resources are about 13 milion tons (the sum of the lithium content in ores and brines). Lepidolite, pedalite, spodumene and amblygonite are the most important minerals containing lithium. Seawater, which contains 230 billion tons of lithium in total, has recently been paid attention as possible resource of this element.

The lithium content in the drinking water is variable from 0.1 ppb to 100 ppm. High lithium concentration is possible to find in some groundwater and mineral waters. Higher concentrations of lithium are also accompanied by higher concentration of sodium usually. The usual lithium concentration in the common surface water is about 10 ppb. Lithium has no limitations in the directives dealing with drinking, surface and supply waters usually. The irrigation waters have the limitation sometimes, since the lithium is cummulated in the plants and inhibit their growth. The limitations vary between 2-5 ppm. The high lithium content in the mineral waters has a balneological impact, since it prevents the risk of the coronary illnesses. Another important impact of lithium content in the drinking waters is a positive influence on the human nervous system; it diminishes some mental diseases accompanying the aggressive manners.

Water source Concentration range in ppm Country
Drinking (surface) 0.002 - 0.017 Czech Republic
Drinking (groundwater) 0.0047 - 0.020 Czech Republic
Drinking (mineral) 0.1 - 13 Czech Republic
Mineral 3-6 Romania
Mineral 4.87-8.00 USA
Volcanic 10-46 Turkey
Volcanic 0.1-44.2 Mexico


Seawater contains about 230 billion tons of lithium (1650 times more than lithium land resources), even though lithium concentration varies between 0.1 - 0.2 ppm. Major sources of lithium in the ocean are hydrothermal interaction between river water and oceanic crust. A tentative mass balance predicates 90 -110 000 tons of Li/year as a river input contribution and 110 - 190 000 tons of Li/year is estimation for hydrothermal input at ridge axes.

Lithium was firstly determined in seawater by Marchand, 1855. He gravimetrically determined 0.2 ppm of lithium concentration in the English Channel. Visual flame spectrometry (Thomas and Thompson, 1933) and spectrographic analyses (Goldschmidt et al., 1933; Strock, 1936) along with precipitation method brought quite inaccurate results varying between 0.072 - 0.14 ppm from the samples taken in North Sea in the forties of the last century. Bardet et al. (1937) removed interfering elements by repeated precipitation and evaporation, together with lithium extraction by amyl alcohol to remove NaCl. This sample from North Atlantic Ocean contained 0.2 ppm. First determination in Pacific Ocean region was carried out by Ishibashi and Kurata (1939). They detected 0.2 ppm of lithium concentration in the sample by evaporation, precipitation and gravimetric method.

Extensive research has been done in the seventies of the 20th century. Chow and Goldberg (1962) took 14 samples in Pacific Region to measure the isotope ratio of 6Li to 7Li. They used mass spectrometry for sample analysis determining average concentration 0.173 ppm. They also found this concentration covariant with chlorinity 8.94 ± 0.12 x 10-6 (in ratio μg Li/kg per Cl ‰). The extensive study was carried out by Riley and Tongudai (1964). They analyzed lithium concentration in all oceans and major seas and also deep seawater. They isolated lithium by ion exchange and determined it by flame photometry. Average lithium concentration from all the samples was about 0.183 ppm and covariant with chlorinity is 9.39 ± 0.17 x 10-6 regardless of the location of the oceans. Angino and Billings (1966) took about 73 samples from North Atlantic and Gulf of Mexico. They determined the average concentration 0.194 ± 0.11 ppm and weak covariance with chlorinity as 9.76 x 10-6. They also observed that concentration profile of lithium decrease gradually but steady with increasing the depth. Hall et al. (2005) studied Li/Cl ratios averaging 9.10 ± 0.11 x 10-6 in Indian Ocean.



Lithium concentration profiles in the seawater- Republic of Palau(A,B) and Fiji (C,D) Lithium concentration profiles in the seawater - Republic of Palau(A,B) and Fiji (C,D)


There are more than 100 known minerals containing lithium. The most lithium rich mineral is griceite containing about 27 wt.% of lithium. However, more than 95 % of lithium recovered from minerals is recovered from spodumene. Next mineral used for the lithium recovery is petalite. Table of the most important minerals together with their physical properties is given in the table below.

Name, Formula Li content Colour                   Hardness Density Luster               Crystal system Diaphaniety Fracture
Spodumene
LiAlSi2O6
3.73 wt.% grayish white, pink, violet, emerald green, yellow 6.5-7 3.1-3.2 vitreous (glassy) monoclinic-prismatic transparent to translucent splintery-thin
Petalite
LiAlSi4O10
2.09 wt.% colorless, gray, yellow, yellow gray, white 6-6.5 2.39-2.46 vitreous-pearly monoclinic-prismatic transparent to translucent brittle-conchoidal
Amblygonite
(Li,Na)AlPO4(F,OH)
3.44 wt. % white, yellow, gray, bluish gray, greenish gray 5.5-6 2.98-3.11 vitreous-pearly triclinic-pinacoidal transparent to subtransparent to translucent uneven
Lepidolite
K(Li,Al)3(Si,Al)4O10(F,OH)2
3.58 wt.% colorless, gray white, lilac, yellowish, white 2.5-3 2.8-2.9 vitreous-pearly monoclinic translucent uneven
Zinnwaldite
KLiFe2+Al(AlSi3)O10(F,OH)2
1.59 wt.% light brown, silvery white, gray, yellowish white, greenish white 3.5-4 0.9-3.1 vitreous-pearly monoclinic-prismatic transparent uneven
Eucryptite
LiAlSiO4
5.51 wt.% brown, colorless, white 6.5 2.67 vitreous (glassy) trigonal-rhomboedral transparent to translucent brittle-conchoidal



Information sources and references cited:

Angino E.E. and G.K. Billings. 1966. Lithium content of seawater by atomic absorption spectrometry. Geochimica et Cosmochimica Acta 30: 153-158.

Bardet J., A. Tchakirian. and R. Lagrange. 1937. Dosage du lithium darts l’eau de mer. Comptes rendus de l’Académie des Sciences 204: 443-445.

Fabricand B.P., E.S. Imbimbo and M.E. Brey. 1967. Atomic absorption analyses for Ca, Li, Mg, K, Rb, and Sr at two Atlantic Ocean stations. Deep Sea Research and Oceanographic Abstracts 14(6): 785-789.

Goldschmidt V. M., H. Berman, H. Hauptman and C. Peters. 1933. Zur Geochemie des Alkalimetalle. Nachrichten von der Königl. Gesellschaft der Wissenschaften zu Göttingen, Mathematisch-Physikalische Klasse 2: 235-238.

Hall J.M., L.H. Chan, W.F. McDonough and K.K. Turekian. 2005. Determination of the lithium isotopic composition of planktic foraminifera and its application as a paleo-seawater proxy. Marine Geology 217: 255-265.

Helvaci C., Mordogan H., Çolak M. and Gündogan I. (2004): Presence and Distribution of Lithium in Borate Deposits and Some Recent Lake Waters of West-Central Turkey, International Geology Review, 46 (2), pp. 177-190.

Ishibashi M. and K. Kurata. 1939. Determination of lithium in sea water and bittern. Journal of Chemical Society Japan 60: 1109-1111.

Lopez T. and Arriaga S. (2000): Geochemical evolution of the Los Azufres, Mexico, Geothermal Reservoir, Part I.: Water and Salts, Proceedings on World Geothermal Congress, Tohoku, Japan.

Marchand E. 1855. Des eaux potables en général. Mémoires de l’Académie Royale de Médecine Paris 19: 121-318.

Pitter (1999): Hydrochemistry, ICT Prague, in Czech: Hydrochemie, VŠCHT Praha.

Riley J.P. and Tongudai M. 1964. The lithium content of sea water. Deep-sea research 11: 563-568.

Stoffyn-Egli P. and F.T. Mackenzie.1984. Mass balance of dissolved lithium in the oceans. Geochimica et Cosmochimica Acta 48: 859-872.

Strock L. W. 1936. Zur Geochemie des Lithium. Nachrichten von der Königl Gesellschaft der Wissenschaften zu Göttingen, Mathematisch-Physikalische Klasse 1: 171-204.

Thomas B. D. and T. Thompson.1933. Lithium in sea water. Science 77: 547-548.

http://minerals.usgs.gov/minerals/pubs/commodity/lithium/

http://webmineral.com/chem/Chem-Li.shtml

http://www.atsdr.cdc.gov/HAC/PHA/foote/foote_p2.html

http://www.biochemsoctrans.org/bst/bs2004/bs2004B201.pdf

http://www.crownminerals.govt.nz/minerals/docs/comreports/report19_beryllium.pdf

http://www.enclabs.com/chart.html

http://www-odp.tamu.edu/publications/201_IR/chap_08/c8_f6.htm#50307


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