Germanium is enriched in the following geologic environments:

• 1.

  (1) iron meteorites and terrestrial iron-nickel;

• 2.

  (2) sulfide ore deposits, particularly those hosted by sedimentary rocks;

• 3.

  (3) iron oxide deposits;

• 4.

  (4) oxidized zones of Ge-bearing sulfide deposits;

• 5.

  (5) pegmatites, greisens, and skarns; and

• 6.

  (6) coal and lignitized wood.

In silicate melts, Ge is highly siderophile in the presence of native iron-nickel; otherwise, it is highly lithophile. Among silicate minerals, Ge is concentrated in those having less polymerized silicate tetrahedra such as olivine and topaz. In deposits formed from hydrothermal solutions, Ge tends to be enriched mostly in either sulfides or in fluorine-bearing phases; it is thus concentrated both in some hydrothermal sulfide deposits and in pegmatites, greisens, and skarns. In sulfide deposits that formed from solutions having low to moderate sulfur activity, Ge is concentrated in sphalerite in amounts up to 3000 ppm. Sulfide deposits that formed from solutions having higher sulfur activity allowed Ge to either form its own sulfides, particularly with Cu, or to substitute for As, Sn, or other metals in sulfosalts. The Ge in hydrothermal fluids probably derives from enrichment during the fractional crystallization of igneous fluids, or is due to the incorporation of Ge from the country rocks, particularly from those containing organic material. Germanium bonds to lignin-derivative organic compounds that are found in peat and lignite, accounting for its common concentration in coals and related organic material. Germanium is precipitated from water together with iron hydroxide, accounting for its concentration in some sedimentary and supergene iron oxide deposits. It also is able to substitute for Fe in magnetite in a variety of geologic environments. In the oxidized zone of Ge-bearing sulfide deposits, Ge is concentrated in oxides, hydroxides, and hydroxy-sulfates, sometimes forming its own minerals. It is particularly enriched in some iron- and manganese-bearing oxides and hydroxides, including goethite (up to 5300 ppm) and hematite (up to 7000 ppm).