Skip to main content

Advertisement

SpringerLink
Log in

Germanium: environmental occurrence, importance and speciation

  • Review Paper
  • Published:
Reviews in Environmental Science and Bio/Technology Aims and scope Submit manuscript

Abstract

This review discusses the various aspects of the bio-geochemistry of germanium, and of its technological, economical and environmental importance. Despite the relatively low annual production and consumption of this semi-metal (ca. 80 metric tons/a) there are important technological applications of this element in the semiconductor, infrared optics and fibre optics/telecommunication industries. A small, but not insignificant fraction of this element is used for the production of pharmaceuticals and nutritional supplements, although its actual merits have not been fully demonstrated yet, while they are opposed to chronic toxicity of the element when being administrated at relatively high doses for an extended period of time. Neither the exact mechanism of action in the case of cancer treatment or the treatment of infectious diseases is known, nor the reason for the toxicity of inorganic species of this element. In plants, Ge can partially substitute for B in the case of boron deficiency, although deficiency symptoms are still seen with a lag period of ca. one to three weeks. In biogeochemical respect, germanium and silicon react very similar, as if Ge were a very heavy isotope of Si. Their molar ratio is typically in the order of 0.6 × 10−6, with significant deviations only where germanium is complexed and transported, e.g., by humic-rich waters. Germanium is a very conservative element in biogeochemical terms: It hardly shows involvement in any biogeochemical reaction cycles and is mainly present in the form of complexes or hydroxo-compounds of the tetravalent germanium. The only naturally occurring organogermanium compounds are mono- and dimethylgermanium which are believed to be formed by microbiological activity in continental zones containing Ge-rich minerals, and then are leached into rivers, and finally into the open sea. It becomes evident that, although very sophisticated technological uses of germanium exist, a better understanding of its biogeochemical importance, cycling and reactivity must still be developed.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9
Fig. 10
Fig. 11
Fig. 12

Similar content being viewed by others

References

  • Adams JH, Thomas D (1994) Germanium and germanium compounds. In: Kirk-Othmer (ed) Encyclopedia of chemical tchnology, vol 12, 4th edn. Wiley, New York, pp 540–555

    Google Scholar 

  • Arnorsson S (1984) Germanium in Islandic geothermal systems. Geochim Cosmochim Acta 48:2482–2502. doi:10.1016/0016-7037(84)90300-4

    Google Scholar 

  • Arroyo F, Fernández-Pereira C (2008) Hydrometallurgical recovery of germanium from coal gasification fly ash solvent extraction method. Ind Eng Chem Res 47:3186–3191. doi:10.1021/ie7016948

    CAS  Google Scholar 

  • Asai K (1977) Organic germanium. A Medical Godsend, Kogakusha

    Google Scholar 

  • Asai K (1980) Miracle cure organic Germanium. Japan publications (out of print). http://www.karlloren.com/ogc/research/books/book1/book1.htm. Accessed May 2008

  • Asai K, Makabe K (1971, 1972) bis-Carboxyethyl germanium sesquioxide and process for preparing same. Japanese patent JP46-2498, 1971, and US Patent US3689516, 1972

  • ASTM (1980) Infrared absorption analysis of impurities in single crystal semiconductor materials. ASTM standard F120–75, American Society for Materials Testing. Annual Book of ASTM Standards, Philadelphia

    Google Scholar 

  • Ayres RU, Holmberg J, Anders B (2001) Materials and the global environment: waste mining in the 21st century. MRS Bull www.mrs.org/publications/bulletin. Accessed June 2001

  • Azam F (1974) Silicic acid uptake in diatoms studies with [68Ge] germanic acid as tracer. Planta 121:205–212. doi:10.1007/BF00389321

    CAS  Google Scholar 

  • Azam F, Hemmingsens BB, Volcani BE (1973) Germanium incoporation into the silica of diatom cell walls. Arch Mikrobiol 92:11–20. doi:10.1007/BF00409507

    CAS  Google Scholar 

  • Babula P, Adam V, Opatrilova R, Zehnalek J, Havel L, Kizek R (2008) Uncommon heavy metals, metalloids and their plant toxicity: a review. Environ Chem Lett 6:189–213. doi10.1007/s10311-008-0159-9

    CAS  Google Scholar 

  • Baukov YI, Tandura SN (2002) Hypervalent compounds of organic germanium, tin and lead derivatives. In: Rappoport Z (ed) Organic germanium, tin and lead compounds, vol 2. Wiley, New York, pp 963–1239

    Google Scholar 

  • Becker JS (2005) Recent developments in isotope analysis by advanced mass spectrometric techniques. J Anal At Spectrom 20:1173–1184. doi:10.1039/b508895j

    CAS  Google Scholar 

  • Bernstein LR (1985) Germanium geochemistry and mineralogy. Geochim Cosmochim Acta 49:2409–2422. doi:10.1016/0016-7037(85)90241-8

    CAS  Google Scholar 

  • BgVV, Bundesamt für gesundheitlichen Verbraucherschutz und Veterinärmedizin (2000) BgVV warnt vor dem Verzehr von Germanium-132 Kapseln. Umweltmed Forsch Prax 5:294

    Google Scholar 

  • Blecker SW, King SL, Derry LA, Chadwick OA, Ippolito JA, Kelly EF (2007) The ratio of germanium to silicon in plant phytoliths: quantification of biological discrimination under controlled experimental conditions. Biogeochem 86:189–199. doi:10.1007/s10533-007-9154-7

    CAS  Google Scholar 

  • Bowen HJM (1996) Trace elements in biochemistry. Academic, London

    Google Scholar 

  • Braman RS, Tompkins MA (1978) Atomic emission spectrometric determination of antimony, germanium, and methylgermanium. Anal Chem 50:1088–1093. doi:10.1021/ac50030a021

    CAS  Google Scholar 

  • Brown RD Jr (2005) USGS mineral commodity profiles: germanium. Reston, Virginia

    Google Scholar 

  • Brown JC, Jones WE (1972) Effect of germanium on utilization of boron in tomato (Lycopersicon esculentum Mill.). Plant Physiol 49:651–653

    CAS  Google Scholar 

  • Bruland KW (1983) Trace elements in sea water. In: Riley JP, Chester R (eds) Chemcal oceanography, vol 8. Academic, London, pp 180–182

    Google Scholar 

  • Célariès B, Gielen M, de Vos D, Rima G (2003) In vitro antitumour activity of some organogermanium radioprotectors. Appl Organomet Chem 17:191–193. doi:10.1002/aoc.403

    Google Scholar 

  • Challenger F (1945) Biological methylation. Chem Rev 36:315–361. doi:10.1021/cr60115a003

    CAS  Google Scholar 

  • Chasteen TG, Bentley R (2003) Biomethylation of selenium and tellurium: microorganisms and plants. Chem Rev 103:1–26. doi:10.1021/cr010210+

    CAS  Google Scholar 

  • Chen R, Liu L, Zhang Z (1995) Synthesis of pentacoordinated germanium compounds containing a phosphonyl group. Heteroatom Chem 6:503–506. doi:10.1002/hc.520060603

    CAS  Google Scholar 

  • Claeys C, Simoen E (2007) Germanium-based technologies. From material to devices. Elsevier, Amsterdam

    Google Scholar 

  • Criaud A, Fouillac AM (1986) Etude des eaux thermominerales carbgazeuses du Massif Central Francais: II. Comportement de quelques metaux en trace, de l’arsenic, de l’antimoine et du germanium. Geochim Cosmochim Acta 50:1573–1582. (in French). doi:10.1016/0016-7037(86)90120-1

  • Czochralski J (1917) Ein neues Verfahren zur Messung der Kristallisationsgeschwindigkeit der Metalle. Z Phys Chem 92:219–221

    CAS  Google Scholar 

  • Dasch EJ (1996) Encyclopedia of earth sciences, vol I. Macmillan, New York, p 563

    Google Scholar 

  • DeArgollo R, Schilling J-G (1978) Ge-Si and Ga-Al fractionation in Hawaiian volcanic rocks. Geochim Cosmochim Acta 42:623–630. doi:10.1016/0016-7037(78)90007-8

    CAS  Google Scholar 

  • Depuydt B, Theuwis A, Romandi I (2006) Germanium: from the first application of Czochralski crystal growth to large diameter dislocation-free wafers. Mater Sci Semicond Process 9:437–443. doi:10.1016/j.mssp.2006.08.002

    CAS  Google Scholar 

  • Deutsche Forschungsgemeinschaft (2005) MAK- und BAT-Werte-Liste 2005. Wiley-VCH, Weinheim

    Google Scholar 

  • Dorr RT, van Hoff DD (1994) Cancer chemotherapy handbook, vol 2. Appleton and Lange, Norwalk

    Google Scholar 

  • Dudley HC, Wallace EJ (1952) Pharmacological studies of radiogermanium (Ge71). Arch Ind Hyg Occup Med 6:263–270

    CAS  Google Scholar 

  • El Wardani SA (1957) On the geochemistry of germanium. Geochim Cosmochim Acta 10:321–322. doi:10.1016/0016-7037(56)90020-5

    Google Scholar 

  • Emmerling G, Schaller KH, Valentin H (1986) Actual knowledge on germanium compounds and feasibility of quantitative determination in occupational medicine and toxicology. Zbl Arbeitsmed 36:258–265

    CAS  Google Scholar 

  • European Commission (2005) Frequently asked questions on directive 2002/95/EC on the restriction of the use of certain hazardous substances in electrical and electronic equipment (RoHS) and directive 2002/96/EC on waste electrical and electronic equipment (WEEE). Available at http://ec.europa.eu/environment/waste/pdf/faq_weee.pdf. Accessed May 2008

  • Faure G (1998) Principles and applications of geochemistry, 2nd edn. Prentice Hall, New Jersey, p 928

    Google Scholar 

  • Fisher BR, Goering PL, Fowler PA (1991) Germanium. In: Merian E (ed) Metals and their compounds in the environment. VCH, Weinheim, pp 921–929

  • Francotte J, Moreau J, Ottenburgs R, Levy C (1965) Briartite, Cu2(Fe, Zn)GeS4, a new mineral. Bull Soc Franc Miner Crist 88:432–437

    CAS  Google Scholar 

  • Froelich PN, Andreae MO (1981) The marine geochemistry of germanium: ekasilicon. Science 213:205–207. doi:10.1126/science.213.4504.205

    CAS  Google Scholar 

  • Froelich PN, Hambrick AS, Kaul LW, Byrd JT, Lecointe O (1985a) Geochemical behaviour of inorganic germanium in an unperturbated estuary. Geochim Cosmochim Acta 49:519–524. doi:10.1016/0016-7037(85)90043-2

    CAS  Google Scholar 

  • Froelich PN, Hambrick GA, Andreae MO, Mortlock RA, Edmond JM (1985b) The geochemistry of inorganic germanium in natural waters. J Geophys Res 90:1133–1141. doi:10.1029/JC090iC01p01133

    CAS  Google Scholar 

  • Froelich PN, Mortlock RA, Shemsh A (1989) Inorganic germanium and silica in the Indian Ocean: biological fractionation during (Ge/Si) opal formation. Global Biogeochem Cycle 3:79–88

    CAS  Google Scholar 

  • Froelich PN, Blanc V, Mortlock RA, Chillrud SN, Dunstan W, Udomkit A, Peng TH (1992) River fluxes of dissolved silica to the ocean were higher during the glacials: Ge/Si in diatoms, rivers, and oceans. Paleoceanography 7:739–768. doi:10.1029/92PA02090

    Google Scholar 

  • Galy A, Pomiès C, Day JA, Pokrovsky OS, Schott J (2003) High precision measurement of germanium isotope ratio variations by multiple collector—inductively coupled plasma mass spectrometry. J Anal At Spectrom 18:115–119. doi:10.1039/b210233a

    CAS  Google Scholar 

  • Gerber GB (1988) Germanium. In: Seiler HG, Sigel H, Sigel A (eds) Handbook on toxicity of inorganic compounds. Marcel Dekker, New York

    Google Scholar 

  • Gerber GB, Léonard A (1997) Mutagenicity, carcinogenicity and teratogenicity of germanium compounds. Mutat Res 387:141–146. doi:10.1016/S1383-5742(97)00034-3

    CAS  Google Scholar 

  • Ginseng UP (2008) Ginseng & Germanium. Available at http://www.ginsengup.com/pages/ginseng/germanium.html. Accessed May 2008

  • Goleva GA, Vorobyeva IN (1967) The migration of germanium in the ground waters of ore deposits. Geochem Int 4:809–817

    Google Scholar 

  • Greenwood NN, Earnshaw A (1984) Chemistry of the elements. Pergamon, Oxford

    Google Scholar 

  • Haller EE (2006) Germanium: from its discovery to SiGe devices. Mater Sci Semicond Process 9:408–422. doi:10.1016/j.mssp.2006.08.063

    CAS  Google Scholar 

  • Haller E, Hansen W, Luke P, Murray R, Jarrel B (1982) Hydrogen concentration and distribution in high-purity germanium crystals. IEEE Trans Nucl Sci NS 29:738–744. doi:10.1109/TNS.1982.4335948

    Google Scholar 

  • Hambrick GA, Froelich PN Jr, Andreae MO, Lewis BL (1984) Determination of methylgermanium species in natural waters by graphite furnace atomic absorption spectrometry with hydride generation. Anal Chem 56:421–424. doi:10.1021/ac00267a027

    CAS  Google Scholar 

  • Hansen W, Haller E, Luke P (1982) Carbon in high-purity germanium. IEEE Trans Nucl Sci NS 29:745–750. doi:10.1109/TNS.1982.4335948

    Google Scholar 

  • Haranczyk C (1975) Morozeviczite and polkovicite, typo-chemical minerals of Mesozoic mineralization of the Fore-Sudenten monocline. Rudy Metalle 20:288–293 (in Polish)

    CAS  Google Scholar 

  • Hernández-Expósito A, Chimenos JM, Fernández JM, Font O, Querol X, Coca P, García Peña F (2006) Ion flotation of germanium from fly ash aqueous leachates. Chem Eng J 118:69–75. doi: 10.1016/j.cej.2006.01.012

    Google Scholar 

  • Hirner AV, Feldmann J, Krupp E, Grümping R, Goguel R, Cullen WR (1998) Metal(loid)organic compounds in geothermal gases and waters. Org Geochem 29:1765–1778. doi:10.1016/S0146-6380(98)00153-3

    CAS  Google Scholar 

  • Höll R, Kling M, Schroll E (2007) Metallogenesis of germanium—a review. Ore Geol Rev 30:145–180. doi:10.1016/j.oregeorev.2005.07.034

    Google Scholar 

  • Hollemann AF, Wiberg E, Wiberg N (1995) Lehrbuch der anorganischen Chemie, 101st edn, de Gruyter, Berlin

    Google Scholar 

  • Housecroft CE, Sharpe AG (2006) Inorganic Chemistry. 3E, 3rd edn, Pearsons Education, Harlow, Essex; UK, Ch. 14

  • Ignatovich L, Zarina D, Shestakova I, Germane S, Lukevics E (2002) Synthesis and biological activity of silyl- and germylsubstituted trifluoroacetylfurans. Met Based Drugs 8:211–214. doi:10.1155/MBD.2001.211

    Google Scholar 

  • Ikemoto K, Kobayashi M, Fukumoto T, Morimatsu M, Pollard RB, Suzuki F (1996) 2-Carboxyethylgermanium sesquioxide, a synthetic organogermanium compound, as an inducer of contrasuppressor T cells. Cell Molecul Life Sci 52:159–166. doi:10.1007/BF01923363

    Article  CAS  Google Scholar 

  • Ishii T, Matsunaga T, Iwai H, Satoh S, Taoshita J (2002) Germanium does not substitute for boron in cross-linking of Rhamnogalacturonan II in pumpkin cell walls. Plant Physiol 130:1967–1973. doi:10.1104/pp009514

    CAS  Google Scholar 

  • Jorgenson JD (2001) Germanium recycling in the United States in 2000, U.S. Geological Survey Circular 1196–V. Available at http://pubs.usgs.gov/circ/c1196v/c1196v.pdf. Accessed May 2008

  • Kaars Sijpesteijn A, Rijkens F, Luijten JGA, Willemsens LC (1962) On the antifungal and antibacterial activity of some trisubstituted organogermanium, organotin and organolead compounds. Antonie Van Leeuwenhoek 28:346–356. doi:10.1007/BF02538746

    Google Scholar 

  • Kaplan BJ, Parish WW, Andrus GM, Simpson JSA, Field CJ (2004a) Germane facts. About germanium sesquioxide: I. Chemistry and anticancer properties. J Altern Complement Med N Y NY 10:337–344. doi:10.1089/107555304323062329

    Google Scholar 

  • Kaplan BJ, Andrus GM, Parish WW (2004b) Germane facts. About germanium sesquioxide: Scientific error and misrepresentation. J Altern Complement Med N Y NY 10:345–348. doi:10.1089/10755530432

    Google Scholar 

  • Karlov SS, Zaitseva GS (2001) Germatranes and their analogs: synthesis, structure and reactivity. Chem Heterocycl Compd 37:1325–1357. doi:10.1023/A:1017942932503

    CAS  Google Scholar 

  • Kluska M (2008) Some aspects of the analysis of biologically active organogermanium substances. Crit Rev Anal Chem 38:84–92. doi:10.1080/10408340701804459

    CAS  Google Scholar 

  • Koga A (1967) Germanium, molybdenum, copper and zinc in New Zealand thermal waters. N Z J Sci 10:428–446

    CAS  Google Scholar 

  • Kraynov SR (1967) Geochemistry of germanium in the thermal carbonate waters (illustrated by examples from the Pamirs and Greater Caucasus). Geochem Int 4:309–320

    Google Scholar 

  • Kresimon J, Grüter U, Hirner A (2001) HG/LT-GC/ICP-MS coupling for identification of metal(loid) species in human urine after fish consumption. Fresenius’ J Anal Chem 371:586–590. doi:10.1007/s002160101087

    CAS  Google Scholar 

  • Kühn R, Birett K (1980) Merkblätter Gefährliche Arbeitsstoffe, vol. 5, Blatt Nr.G06, Verlag Moderne Industrie, München

  • Kurtz AC, Derry LA, Chadwick OA (2002) Germanium-silicon fractionation in the weathering environment. Geochim Cosmochim Acta 66:1525–1537. doi:10.1016/S0016-7037(01)00869-9

    CAS  Google Scholar 

  • Landolt-Börnstein (2002) Group IV Elements, IV-IV and III-V Compounds. Part b—Electronic, Transport, Optical and Other Properties. Madelung O, Rössler U, Schulz M (eds) Springer, Heidelberg, vol 41A1b, pp 1–10

  • Landon RE, Mogilnor AH (1933) Colusite, a new mineral of the sphalerite group. Am Mineral 18:528–533

    CAS  Google Scholar 

  • Laznicka P (1999) Quantitative relationships among giant deposits of metals. Econ Geol 94:455–473

    CAS  Google Scholar 

  • Lewis BL, Mayer HP (1993) Metal ions in biological systems. In: Sigel A (ed) Biological properties of metal alkyl derivatives. Marcel Dekker, Basel, pp 79–99

    Google Scholar 

  • Lewis BL, Andreae MO, Froelich PN (1988a) The biogeochemistry of methylgermanium spcies: a review. In: Craig PJ, Glocking F (eds) The biological alkylation of heavy metals. The Royal Society of Chemistry, London, pp 77–91

    Google Scholar 

  • Lewis BL, Andreae MO, Froelich PN, Mortlock RA (1988b) A review of the biogeochemistry of germanium in natural waters. Sci Total Environ 73:107–120. doi:10.1016/0048-9697(88)90191-X

    CAS  Google Scholar 

  • Lewis BL, Andreae MO, Froelich PN (1989) Sources and sinks of methylgermanium in natural waters. Mar Chem 27:179–200. doi:10.1016/0304-4203(89)90047-9

    CAS  Google Scholar 

  • Lombaard AF, Günzel A, Innes A, Krüger TL (1986) Tsumeb lead–copper–zinc–silver deposit, South West Africa/Namibia. In: Anhaeusser CR, Maske S (eds) Mineral deposits of Southern Africa, vol 2. Geol Soc South Africa, Johannesburg, pp 1761–1782

    Google Scholar 

  • Lucent Technologies (1997) Innovative germanium-recovery process from Bell Labs is economically and environmentally friendly. News release, Lucent Technologies, Atlanta, October 16, p 1

  • Lück BE, Mann H, Melzer H, Dunemann L, Bergerow J (1999) Renal and other organ failure caused by germanium intoxication. Nephrol Dial Transplant 14:2464–2468

    Google Scholar 

  • Lukevics E, Ignatovich L (1992) Comparative study of the biological activity of organosilicon and organogermanium compounds. Appl Organomet Chem 6:113–126. doi:10.1002/aoc.590060204

    CAS  Google Scholar 

  • Lukevics E, Ignatovich L (2002) Biological activity of organogermanium compounds. In: Rappoport Z (ed) The chemistry of organic germanium, tin and lead compounds. Wiley, Chichester, pp 1653–1683

    Google Scholar 

  • Lukevics E, Ignatovich L (2005) 32Ge biological activity of organogermanium compounds. In: Gielen M, Tiekink ERT (eds) Metallotherapeutic drugs and metal-based diagnostic agents. Wiley, Chichester, pp 279–295

    Google Scholar 

  • Lukevics E, Germane S, Ignatovich L (1992) Neurotropic activity of organogermanium compounds. Appl Organomet Chem 6:543–564. doi:10.1002/aoc.590060702

    CAS  Google Scholar 

  • Market Prices (2003) Rare earths and specialty metals market prices. Internet source, August, 1 p. Accessed May 2008

  • McIllrath WJ, Skok J (1966) Substitution of germanium for boron in plant growth. Plant Physiol 41:1209–1212

    Google Scholar 

  • McMahon M, Regan F, Hughes H (2007) The determination of total germanium in real food samples including Chinese herbal remedies using graphite furnace atomic absorption spectroscopy. Food Chem 97:411–417. doi:10.1016/j.foodchem.2005.05.018

    Google Scholar 

  • Mehard CW, Volcani BE (1975) Similarity in uptake and retention of trace amounts of 31Si and 68Ge in rat tissues and cell organelles. Bioinorg Chem 5:107–124. doi:10.1016/S0006-3061(00)80055-1

    CAS  Google Scholar 

  • Mehard CW, Sullivan CW, Azam F, Volcani BE (1974) Role of silicon in diatom metabolism: IV Subcellular localization of silicon and germanium in Nitzschia alba and Cylindrotheca fusiformis. Physiol Plant 30:265–272. doi:10.1111/j.1399-3054.1974.tb03654.x

    CAS  Google Scholar 

  • Melcher F (2003) The Otavi mountain land in Namibia: Tsumeb, germanium and snowball earth. Mitt Österr Mineralog Ges 148:413–435

    Google Scholar 

  • Mendelejew D (1871) Die periodische Gesetzmäßigkeit der chemischen Elemente. Ann Chem Pharm Leipzig 871(Suppl VIII):133

    Google Scholar 

  • Mironov VF, Berliner EM, Gar TK (1967) Reaction of trichlorogermane with acrylic acid and its derivatives. Zh Obshch Khim 37:962 (in Russian)

    CAS  Google Scholar 

  • Mironov VF, Berliner EM, Gar TK, Rybakov EA (1968) Reaction of trichlorogermane with unsaturated carboxylic acids. Zh Obshch Khim 38:2292–2300 (in Russian)

    CAS  Google Scholar 

  • Morita H, Shimomura S, Odagawa K, Saito S, Sakigawa C, Sato H (1986) Determination of germanium and some other elements in hair and toe nail from persons exposed and unexposed to germanium. Sci Total Environ 58:237–242. doi:10.1016/0048-9697(86)90203-2

    CAS  Google Scholar 

  • Mortlock RA, Froelich PN (1986) Hydrothermal germanium over the southern East Pacific Rise. Science 231:43–45. doi:10.1126/science.231.4733.43

    CAS  Google Scholar 

  • Mortlock RA, Froelich PN (1987) Continental weathering of germanium: Ge/Si in the global river discharge. Geochim Cosmochim Acta 51:2075–2082. doi:10.1016/0016-7037(87)90257-2

    CAS  Google Scholar 

  • Moskalyk RR (2004) Review of germanium processing worldwide. Miner Eng 17:393–402. doi:10.1016/j.mineng.2003.11.014

    CAS  Google Scholar 

  • MSDS (2005) Material safety data sheet germanium tetrachloride, Available at http://agrippina.bcs.deakin.edu.au/bcs_admin/msds/msds_docs/Germanium%20(IV)%20chloride.pdf. Accessed May 2008

  • Murnane RJ, Stallard RF (1990) Germanium and silicon in rivers of the Orinoco drainage basin. Nature 344:749–752. doi:10.1038/344749a0

    CAS  Google Scholar 

  • Nagata N, Yoneyama T, Yanagida K, Ushio K, Yanagihara S, Matsubara O, Eishi Y (1985) Accumulation of germanium in the tissues of a long-term user of germanium preparation died of acute renal failure. J Toxicol Sci 10:333–341

    CAS  Google Scholar 

  • Nikolic M, Nikolic N, Liang YC, Kirkby EA, Romheld V (2007) Germanium-68 as an adequate tracer for silicon transport in characterization of silicon uptake in different crop species. Plant Physiol 143:495–503. doi:10.1104/pp106090845

    CAS  Google Scholar 

  • Nuriyev AN, Lapshina NF, Dzhabarova ZA (1968) Germanium in oil, water and rocks of oil deposits. Geochem Int 5:911–915

    Google Scholar 

  • Omae I (1999) Applications of organometallic compounds. Wiley, chichester, pp 165–184

    Google Scholar 

  • Parish D (2005) Germanium sesquioxide, organic germanium, Bis(2-Carboxyethylgermanium)sesquioxide, Available at http://www.germaniumsesquioxide.com. Accessed May 2008

  • Penfield SL (1984) Canfieldite, a new germanium mineral. Am J Sci 46:107–113

    Google Scholar 

  • Pokrovski GS, Schott J (1998a) Experimental study of the complexation of silicon and germanium with aqueous organic species: Implications for germanium and silicon transport and Ge/Si ratio in natural waters. Geochim Cosmochim Acta 62:3413–3428. doi:10.1016/S0016-7037(98)00249-X

    CAS  Google Scholar 

  • Pokrovski GS, Schott J (1998b) Thermodynamic properties of aqueous Ge(IV) hydroxide complexes from 25 to 350°C: implications for the behaviour of germanium and the Ge/Si ratio in hydrothermal fluids. Geochim Cosmochim Acta 62:1631–1642. doi:10.1016/S0016-7037(98)00081-7

    CAS  Google Scholar 

  • Pokrovsky OS, Schott J (2002) Iron colloids/organic matter associated transport of major and trace elements in small boreal rivers and their estuaries (NW Russia). Chem Geol 190:141–179. doi:10.1016/S0009-2541(02)00115-8

    CAS  Google Scholar 

  • Pokrovski GS, Martin F, Hazemann J-L, Schott J (2000) An X-ray absorption fine structure spectroscopy study of germanium-organic ligand complexes in aqueous solution. Chem Geol 163:151–165. doi:10.1016/S0009-2541(99)00102-3

    CAS  Google Scholar 

  • Pokrovsky OS, Pokrovski GS, Schott J, Galy A (2006) Experimental study of germanium adsorption on goethite and germanium coprecipitation with iron hydroxide: X-ray absorption fine structure and macroscopic characterization. Geochim Cosmochim Acta 70:3325–3341. doi:10.1016/j.gca.2006.04.012

    CAS  Google Scholar 

  • Pufahl O (1922) Germanite, a germanium mineral and ore from Tsumeb, Southwest Africa. Metall Erz 19:324

    CAS  Google Scholar 

  • Putz H, Paar WH, Topa D, Makovický E, Roberts AC (2006) Catamarcait, Cu6GeWS8, a new species of germanium–tungsten-sulphide from Capillitas, Catamarca, Argentinia: description, paragenesis and crystal structure. Can Mineral 44:1481–1497. doi:10.2113/gscanmin.44.6.1481

    CAS  Google Scholar 

  • Reimann C, de Caritat P (1998) Chemical elements in the environment. Springer, Berlin, p 398

    Google Scholar 

  • Rinkevich B (1986) Does germanium interact with radular morphogenesis and biomineralization in the limpet Lottia gigantea? Comp Biochem Physiol C83:137–141

    Google Scholar 

  • Riviere P, Riviere-Baudet M, Satge J (1982) In: Wilkinson G, Stone FGA, Abel EW (eds) Comprehensive organometallic chemistry. Pergamon Press, Oxford, vol 2, 399 pp

  • Rochow EG (1947) Organic compounds of germanium. The direct synthesis from elementary germanium. J Am Chem Soc 69:1729–1731. doi:10.1021/ja01199a046

    CAS  Google Scholar 

  • Roels HA, Buchet J-P (2001) Determination of germanium in urine and its usefulness for biomonitoring of inhalation exposure to inorganic germanium in the occupational setting. J Environ Monit 3:67–73. doi:10.1039/b007132n

    CAS  Google Scholar 

  • Rosenberg E (2007) Environmental speciation of germanium. Ecol Chem Eng 14:707–732

    CAS  Google Scholar 

  • Rosenfeld G, Wallace EJ (1953) Studies of the acute and chronic toxicity of germanium. AMA Arch Ind Health 8:466–479

    CAS  Google Scholar 

  • Rouxel O, Galy A, Elderfield H (2006) Germanium isotopic variations in igneous rocks and marine sediments. Geochim Cosmochim Acta 70:3387–3400. doi:10.1016/j.gca.2006.04.025

    CAS  Google Scholar 

  • Santosa SJ, Wada S, Mokudai H, Tanaka S (1997) The contrasting behaviour of arsenic and germanium species in seawater. Appl Organomet Chem 11:403–414. doi:10.1002/(SICI)1099-0739(199705)11:5<403::AID-AOC596>3.0.CO;2-4

    CAS  Google Scholar 

  • Schauss AG (1991) Nephrotoxicity in humans by the ultratrace element germanium. Ren Fail 13:1–4. doi:10.3109/08860229109022139

    CAS  Google Scholar 

  • Schroeder HA, Balassa JJ (1967a) Arsenic, germanium, tin and vanadium in mice: effects on growth, survival and tissue levels. J Nutr 92:245–252

    CAS  Google Scholar 

  • Schroeder HA, Balassa JJ (1967b) Abnormal trace metal in man: germanium. J Chronic Dis 20:221–224

    Google Scholar 

  • Scoyer J, Guislain H, Wolf HU (2005) Germanium and germanium compounds. In: Ullmann’s encyclopedia of industrial chemistry. 5th edn, Wiley-VCH, Weinheim, (Electronic edition)

  • Scribner AM, Kurtz AC, Chadwick OA (2006) Germanium sequestration by soil: targeting the roles of secondary clays and Fe-oxyhydroxides. Earth Planet Sci Lett 243:760–770. doi:10.1016/j.epsl.2006.01.051

    CAS  Google Scholar 

  • Selina AA, Karlov SS, Zaitseva GS (2006) Metallocanes of group 14 elements. 1. derivatives of silicon and germanium. (Review). Chem Heterocycl Compd 42:1518–1556. doi:10.1007/s10593-006-0278-9

  • Shangguan G, Xing F, Qu X, Mao J, Zhao D, Zhaob X, Ren J (2005) DNA binding specificity and cytotoxicity of novel antitumor agent Ge132 derivatives. Bioorg Med Chem Lett 15:2962–2965. doi:10.1016/j.bmcl.2005.04.053

    CAS  Google Scholar 

  • Simpson TL, Garrone R, Mazzorana M (1983) Interaction of germanium (Ge) with biosilicification in the freshwater sponge Ephydatia mülleri: evidence of localized membrane domains in the silicalemma. J Ultrastruct Res 85:159–174. doi:10.1016/S0022-5320(83)90104-1

    CAS  Google Scholar 

  • Skok J (1957) The substitution of complexing substances for boron in plant growth. Plant Physiol 32:308–312

    CAS  Google Scholar 

  • Slawson RM, Van Dyke MI, Lee H, Trevors JT (1992) Germanium and silver resistance, accumulation, and toxicity in microorganisms. Plasmid 27:72–79. doi:10.1016/0147-619X(92)90008-X

    CAS  Google Scholar 

  • Spectrum (2003) Chemical fact sheet for germanium. Spectrum Laboratories, Ft. Lauderdale, FL, p 4

  • Spiridonov EM (2003) Maikainite Cu20(Fe, Cu)6Mo2Ge6S32 and ovamboite Cu20(Fe, Cu, Zn)6W2Ge6S32: new minerals in massive sulfide base metal ores. Dokl Earth Sci 393:1329–1332 (in Russian)

    Google Scholar 

  • Spiridonov EM, Kachalovskaya VM, Kovachev VV, Krapiva LY (1992) Germanocolusite Cu26V2(Ge, As)6S32—a new mineral. Vestnik Moskovskogo Universiteta, Ser. 4. Geologiya 6:50–54 (in Russian)

    Google Scholar 

  • Strunz H, Tennyson C (1967) Schaurteit, ein neues Germaniun-Mineral von Tsumeb/SW-Afrika und seine Paragenese. In: Festschrift Dr. Werner Schaurte. Bauer H, Schaurte W (eds) Neuss/Rhein (Germany), pp 33–47 (in German)

  • Strunz H, Sohnge G, Geier BH (1958) Stottite, a new germanium mineral, and its paragenesis at Tsumeb. Neues Jahrb f Mineralog, Monatsh pp 85–96 (in German)

  • Swennen B, Mallants A, Roels HA, Buchet JP, Bernard A, Lauwerys RR, Lison D (2000) Epidemiological survey of workers exposed to inorganic germanium compounds. Occup Environ Med 57:242–248. doi:10.1136/oem.57.4.242

    CAS  Google Scholar 

  • Takakusaki K, Kakimoto N, Takeuchi Y, Tomoda S (1983) Synthesis of germanium derivatives of uracil and 5-fluorouracil. Tetrahedron Lett 24:1707–1710. doi:10.1016/S0040-4039(00)81750-5

    CAS  Google Scholar 

  • Takeuchi Y, Nishikawa M, Tanaka K, Yamamoto G (2001) Dynamic behavior of pentacoordinate organogermanium carboxylic acids and their pyridinium salts. Heteroatom Chem 12:451–456. doi:10.1002/hc.1067

    CAS  Google Scholar 

  • Takeuchi Y, Nishikawa M, Yamamoto H (2004) High-resolution solid-state 73Ge NMR spectra of hexacoordinated germanium compounds. Magn Reson Chem 42:907–909. doi:10.1002/mrc.1486

    CAS  Google Scholar 

  • Tao S-H, Bolger PM (1997) Hazard assessment of germanium supplements. Regul Toxicol Pharmacol 25:211–219. doi:10.1006/rtph.1997.1098

    CAS  Google Scholar 

  • Taylor SR, McLennan SM (1985) The continental crust: its composition and evolution. Blackwell, Oxford, p 312

    Google Scholar 

  • Thayer JS (1987) Germapharmaca: some recent studies on biologically active organogermanium compounds. Appl Organomet Chem 1:227–234. doi:10.1002/aoc.590010303

    CAS  Google Scholar 

  • Thayer JS (2002) Biological methylation of less-studied elements. Appl Organomet Chem 16:677–691. doi:10.1002/aoc.375

    CAS  Google Scholar 

  • Tsutui M, Kakimoto N, Axtell DD, Oikawa H, Asai K (1976) Crystal structure of carboxyethylgermanium sesquioxide. J Am Chem Soc 98:8287–8289. doi:10.1021/ja00441a081

    Google Scholar 

  • USGS (1992) Germanium: mineral commodity summaries. January 1992. US. Geological survey. Denver, USA

    Google Scholar 

  • USGS (2000) US geological survey and US department of the interior, Germanium recycling in the United States in 2000, US. Geological Survey Circular 1196–V, internet source, 15 pp

  • USGS (2003) Germanium: mineral commodity summaries. January 2003. US. Geological Survey, Denver, CO, USA

  • USGS (2007a), Germanium: mineral commodity statistics. In: Kelly TD, Matos GR (comps) Historical statistics for mineral and material commodities in the United States: US. Geological Survey Data Series 140. Available at http://minerals.usgs.gov/ds/2005/140/. Accessed May 2008

  • USGS (2007b) Germanium: mineral commodity summaries. January 2007. U.S. Geological Survey, Denver, CO, USA, 68–69. Available at http://minerals.usgs.gov/minerals/pubs/mcs/2007/mcs2007.pdf. Accessed May 2008

  • Vaes JF (1948) La reniérite (anciennement appelée “bornite orange”) un sulfure germanifère provenant de la Mine Prince-Léopold, Kipushi (Congo Belge). Ann (Bull) Soc Géol Belgique 72: 20–32 (in French)

    Google Scholar 

  • van Ass HMJM, Geittner P, Gossink RG, Kuppers D, Severin PJW (1976) Manufacture of glass fibres for optical communication. Philips Techn Rev 36:182–189

    Google Scholar 

  • Vetter K (2007) Recent developments in the fabrication and operation of germanium detectors. Ann Rev Nucl Part Sci 57:363–404. doi:10.1146/annurev.nucl.56.080805.140525

    CAS  Google Scholar 

  • Voronkov MG, Abzaeva KA (2002) Genesis and evolution in the chemistry of organogermanium, organotin and organolead compounds. In: Rappoport Z (ed) The chemistry of organic germanium, tin and lead compounds, vol 2. Wiley, Chichester, pp 1–130

    Google Scholar 

  • Webster SH (1946) Volatile hydrides of toxicological importance. J Ind Hyg Toxicol 28:167–182

    CAS  Google Scholar 

  • Weisbach A (1886) Argyrodit, ein neues Silbererz. Neues Jahrbuch für Mineralogie, Geologie und Paläontologie. II. Band. pp 67–71

  • Winkler C (1886a) Germanium, Ge, ein neues, nichtmetallisches Element. Ber Dt Chem Ges 19:210–211. doi:10.1002/cber.18860190156

    Google Scholar 

  • Winkler C (1886b) Mittheilungen über das Germanium. J Prakt Chem 34:177–229. doi:10.1002/prac.18860340122

    Google Scholar 

  • Winkler C (1887) Über das Germanium, dessen Nachweis und Bestimmung. Fresenius Z Anal Chem 26:359–364. doi:10.1007/BF01385208

    Google Scholar 

  • Wolf K-H, Küster B, Herlinger H, Tschang C-J, Schollmeyer E (1978) Metallkatalysatoren in der Herstellung von Polyäthylenterephthalat. 2. Ermittlung von Parametern zur Beschreibung der katalytischen Aktivität von Metallverbindungen in Polykondensationsreaktionen. Angew Makromol Chem 68:23–37. doi:10.1002/apmc.1978.050680103

    CAS  Google Scholar 

  • Wood SA, Samson IM (2006) The aqueous geochemistry of gallium, germanium, indium and scandium. Ore Geol Rev 28:57–102. doi:10.1016/j.oregeorev.2003.06.002

    Google Scholar 

  • Yang SJ, Rafla S (1983) Effect of spirogermanium on V79 Chinese hamster cells. Am J Clin Oncol 6:331–337. doi:10.1097/00000421-198306000-00014

    CAS  Google Scholar 

  • Yashiki Y, Miyajima S, Yamada A, Konagai M (2006) Deposition and characterization of μc-Ge1-xCx thin films grown by hot-wire chemical vapor deposition using organo-germane. Thin Solid Films 501:202–205. doi:10.1016/j.tsf.2005.07.174

    CAS  Google Scholar 

  • Ysart G, Miler P, Crews H, Robb P, Baxter M, De L’Argy C, Lofthouse S, Sargent C, Harrison N (1999) Dietary exposure estimates of 30 elements from the UK Total Diet Study. Food Addit Contam 16:391–403. doi:10.1080/026520399283876

    CAS  Google Scholar 

  • Zaijun L, Jian T, Huizhen L, Xia Z, Rui Y (2007) Determination of trace amounts of germanium in food and fruit by spectrophotometry with p-methybenzeneazosalicylflurone. J Food Compost Anal 20:1–6. doi:10.1016/j.jfca.2006.04.009

    Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Institute of Chemical Technologies and Analytics, Vienna University of Technology, Getreidemarkt 9/164 AC, 1060, Vienna, Austria

    Erwin Rosenberg

Authors
  1. Erwin Rosenberg
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Erwin Rosenberg.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Rosenberg, E. Germanium: environmental occurrence, importance and speciation. Rev Environ Sci Biotechnol 8, 29–57 (2009). https://doi.org/10.1007/s11157-008-9143-x

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11157-008-9143-x

Keywords

Search

Navigation