Gallium: Professional Paper 1802-H

Gallium
Chapter H of
Critical Mineral Resources of the United States—Economic and
Environmental Geology and Prospects for Future Supply
Professional Paper 1802–H
U.S. Department of the Interior

U.S. Geological Survey
Periodic Table of Elements
1A 8A
1 2
hydrogen helium
1.008 2A 3A 4A 5A 6A 7A 4.003
3 4 5 6 7 8 9 10
lithium beryllium boron carbon nitrogen oxygen fluorine neon

6.94 9.012 10.81 12.01 14.01 16.00 19.00 20.18
11 12 13 14 15 16 17 18
sodium magnesium aluminum silicon phosphorus sulfur chlorine argon

22.99 24.31 3B 4B 5B 6B 7B 8B 11B 12B 26.98 28.09 30.97 32.06 35.45 39.95
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
potassium calcium scandium titanium vanadium chromium manganese iron cobalt nickel copper zinc gallium germanium arsenic selenium bromine krypton
39.10 40.08 44.96 47.88 50.94 52.00 54.94 55.85 58.93 58.69 63.55 65.39 69.72 72.64 74.92 78.96 79.90 83.79
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
rubidium strontium yttrium zirconium niobium molybdenum technetium ruthenium rhodium palladium silver cadmium indium tin antimony tellurium iodine xenon
85.47 87.62 88.91 91.22 92.91 95.96 (98) 101.1 102.9 106.4 107.9 112.4 114.8 118.7 121.8 127.6 126.9 131.3
55 56 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
cesium barium hafnium tantalum tungsten rhenium osmium iridium platinum gold mercury thallium lead bismuth polonium astatine radon
132.9 137.3 178.5 180.9 183.9 186.2 190.2 192.2 195.1 197.0 200.5 204.4 207.2 209.0 (209) (210) (222)
87 88 104 105 106 107 108 109 110 111 112 113 114 115 116 117 118
francium radium rutherfordium dubnium seaborgium bohrium hassium meitnerium darmstadtium roentgenium copernicium flerovium livermorium
(223) (226) (265) (268) (271) (270) (277) (276) (281) (280) (285) (284) (289) (288) (293) (294) (294)
57 58 59 60 61 62 63 64 65 66 67 68 69 70 71
Lanthanide Series*
lanthanum cerium praseodymium neodymium promethium samarium europium gadolinium terbium dysprosium holmium erbium thulium ytterbium lutetium
138.9 140.1 140.9 144.2 (145) 150.4 152.0 157.2 158.9 162.5 164.9 167.3 168.9 173.0 175.0
89 90 91 92 93 94 95 96 97 98 99 100 101 102 103

Actinide Series**
actinium thorium protactinium uranium neptunium plutonium americium curium berkelium californium einsteinium fermium mendelevium nobelium lawrencium
(227) 232 231 238 (237) (244) (243) (247) (247) (251) (252) (257) (258) (259) (262)
element names in blue are liquids at room temperature

element names in red are gases at room temperature
element names in black are solids at room temperature
Modified from Los Alamos National Laboratory Chemistry Division; available at http://periodic.lanl.gov/images/periodictable.pdf.
Cover. Photographs showing samples of bauxite ore and sphalerite ore, which are the primary mineralogical sources of gallium. Gallium is
used in a variety of products from smartphones to experimental cars, also shown. Photograph of experimental car courtesy of the University
of Michigan; used with permission.
Gallium
By Nora K. Foley, Brian W. Jaskula, Bryn E. Kimball, and Ruth F. Schulte
Chapter H of
Critical Mineral Resources of the United States—Economic and
Environmental Geology and Prospects for Future Supply
Edited by Klaus J. Schulz, John H. DeYoung, Jr., Robert R. Seal II, and Dwight C. Bradley
Professional Paper 1802– H

RYAN K. ZINKE, Secretary

William H. Werkheiser, Acting Director
U.S. Geological Survey, Reston, Virginia: 2017
For more information on the USGS—the Federal source for science about the Earth, its natural and living
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visit https://store.usgs.gov/.
Any use of trade, firm, or product names is for descriptive purposes only and does not imply endorsement by the
U.S. Government.
Although this information product, for the most part, is in the public domain, it also may contain copyrighted materials
as noted in the text. Permission to reproduce copyrighted items must be secured from the copyright owner.
Suggested citation:
Foley, N.K., Jaskula, B.W., Kimball, B.E., and Schulte, R.F., 2017, Gallium, chap. H of Schulz, K.J., DeYoung, J.H., Jr.,
Seal, R.R., II, and Bradley, D.C., eds., Critical mineral resources of the United States—Economic and environ-
mental geology and prospects for future supply: U.S. Geological Survey Professional Paper 1802, p. H1– H35,
https://doi.org/10.3133/pp1802H.
ISSN 2330-7102 (online)

iii
Contents
Abstract.........................................................................................................................................................H1
Introduction..................................................................................................................................................H1
Strategic and Critical Resource Issues..........................................................................................H2
Uses and Applications.......................................................................................................................H2
Geology..........................................................................................................................................................H6
Geochemistry......................................................................................................................................H6
Mineralogy.........................................................................................................................................H12
Gibbsite-Diaspore-Boehmite.................................................................................................H14
Sphalerite..................................................................................................................................H15
Deposit Types....................................................................................................................................H15
Bauxite Deposits......................................................................................................................H15
Sediment-Hosted Lead-Zinc Deposits.................................................................................H18
Clastic-Dominated Lead-Zinc Type..............................................................................H19
Mississippi Valley Lead-Zinc Type...............................................................................H19
Kipushi Polymetallic Type..............................................................................................H20
Resources and Production.......................................................................................................................H21
Identified Resources........................................................................................................................H21
Undiscovered Resources................................................................................................................H21
Production..........................................................................................................................................H21
Exploration for New Deposits..................................................................................................................H22
Environmental Considerations.................................................................................................................H22
Sources and Fate in the Environment...........................................................................................H22
Mine Waste Characteristics...........................................................................................................H23
Human Health Concerns..................................................................................................................H24
Ecological Health Concerns............................................................................................................H24
Carbon Footprint...............................................................................................................................H25
Mine Closure.....................................................................................................................................H25
Problems and Future Research...............................................................................................................H26
References Cited.......................................................................................................................................H26
iv
Figures
H1. Photograph of gallium metal with an inset showing its position on the periodic
table of elements........................................................................................................................H1
H2. Photographs showing examples of some current uses for gallium...................................H3
H3. Charts showing U.S. and world gallium production and consumption from 2007
to 2012...........................................................................................................................................H4
H4. World map showing locations of selected mineral deposits, by type; gallium
has been produced from these types of deposits.................................................................H5
H5. Cross sections showing the general geologic environments for the types of
mineral deposits with which gallium is most commonly associated and from
which gallium is typically extracted........................................................................................H6
H6. Plot of the ratio of aluminum to gallium versus gallium content for bauxite
deposits, volcanic rocks, and hydrothermally altered rocks of the
McDermitt caldera, Nevada...................................................................................................H12
H7. Photographs showing samples of bauxite ore and sphalerite ore, which are the
primary mineralogical sources of gallium............................................................................H14
Tables
H1. Selected properties of gallium, a Group 13 post-transition metal......................................H8
H2. Gallium concentrations in rocks, ore, coal, soils, and natural waters..............................H9
H3. Selected gallium-bearing minerals—Formula, content, and occurrence......................H13
H4. Significant global and domestic deposit types from which gallium is obtained
or is potentially extractable....................................................................................................H16
v
Conversion Factors
International System of Units to Inch/Pound
Multiply By To obtain
Length
angstrom (Å) (0.1 nanometer) 0.003937 microinch
angstrom (Å) (0.1 nanometer) 0.000003937 mil
micrometer (µm) [or micron] 0.03937 mil
millimeter (mm) 0.03937 inch (in.)
centimeter (cm) 0.3937 inch (in.)
meter (m) 3.281 foot (ft)
meter (m) 1.094 yard (yd)
kilometer (km) 0.6214 mile (mi)
Area
hectare (ha) 2.471 acre
square kilometer (km2) 247.1 acre
square meter (m2) 10.76 square foot (ft2)
square centimeter (cm2) 0.1550 square inch (ft2)
square kilometer (km2) 0.3861 square mile (mi2)
Volume
milliliter (mL) 0.03381 ounce, fluid (fl. oz)
liter (L) 33.81402 ounce, fluid (fl. oz)
liter (L) 1.057 quart (qt)
liter (L) 0.2642 gallon (gal)
cubic meter (m3) 264.2 gallon (gal)
cubic centimeter (cm3) 0.06102 cubic inch (in3)
cubic meter (m3) 1.308 cubic yard (yd3)
cubic kilometer (km3) 0.2399 cubic mile (mi3)
Mass
microgram (μg) 0.00000003527 ounce, avoirdupois (oz)
milligram (mg) 0.00003527 ounce, avoirdupois (oz)
gram (g) 0.03527 ounce, avoirdupois (oz)
gram (g) 0.03215075 ounce, troy
kilogram (kg) 32.15075 ounce, troy
kilogram (kg) 2.205 pound avoirdupois (lb)
ton, metric (t) 1.102 ton, short [2,000 lb]
ton, metric (t) 0.9842 ton, long [2,240 lb]
Deposit grade
gram per metric ton (g/t) 0.0291667 ounce per short ton (2,000 lb) (oz/T)
Pressure
megapascal (MPa) 10 bar
gigapascal (GPa) 10,000 bar
Density
gram per cubic centimeter (g/cm3) 62.4220 pound per cubic foot (lb/ft3)
milligram per cubic meter (mg/m3) 0.00000006243 pound per cubic foot (lb/ft3)
Energy
joule (J) 0.0000002 kilowatthour (kWh)
joule (J) 6.241 × 1018 electronvolt (eV)
joule (J) 0.2388 calorie (cal)
kilojoule (kJ) 0.0002388 kilocalorie (kcal)
vi
International System of Units to Inch/Pound—Continued

Multiply By To obtain
Radioactivity
becquerel (Bq) 0.00002703 microcurie (μCi)
kilobecquerel (kBq) 0.02703 microcurie (μCi)
Electrical resistivity
ohm meter (Ω-m) 39.37 ohm inch (Ω-in.)
ohm-centimeter (Ω-cm) 0.3937 ohm inch (Ω-in.)
Thermal conductivity
watt per centimeter per degree 693.1798 International British thermal unit
Celsius (watt/cm °C) inch per hour per square foot per
degree Fahrenheit (Btu in/h ft2 °F)
watt per meter kelvin (W/m-K) 6.9318 International British thermal unit
inch per hour per square foot per
degree Fahrenheit (Btu in/h ft2 °F)
Inch/Pound to International System of Units

Length
mil 25.4 micrometer (µm) [or micron]
inch (in.) 2.54 centimeter (cm)
inch (in.) 25.4 millimeter (mm)
foot (ft) 0.3048 meter (m)
mile (mi) 1.609 kilometer (km)
Volume
ounce, fluid (fl. oz) 29.57 milliliter (mL)
ounce, fluid (fl. oz) 0.02957 liter (L)
Mass
ounce, avoirdupois (oz) 28,350,000 microgram
ounce, avoirdupois (oz) 28,350 milligram
ounce, avoirdupois (oz) 28.35 gram (g)
ounce, troy 31.10 348 gram (g)
ounce, troy 0.03110348 kilogram (kg)
pound, avoirdupois (lb) 0.4536 kilogram (kg)
ton, short (2,000 lb) 0.9072 ton, metric (t)
ton, long (2,240 lb) 1.016 ton, metric (t)
Deposit grade
ounce per short ton (2,000 lb) (oz/T) 34.285714 gram per metric ton (g/t)
Energy
kilowatthour (kWh) 3,600,000 joule (J)
electronvolt (eV) 1.602 × 10–19 joule (J)
Radioactivity
microcurie (μCi) 37,000 becquerel (Bq)
microcurie (μCi) 37 kilobecquerel (kBq)
Temperature in degrees Celsius (°C) may be converted to degrees Fahrenheit (°F) as follows:
°F = (1.8 × °C) + 32
Temperature in degrees Celsius (°C) may be converted to kelvin (K) as follows:
K = °C + 273.15
Temperature in degrees Fahrenheit (°F) may be converted to degrees Celsius (°C) as follows:
°C = (°F – 32) / 1.8
vii
Datum
Unless otherwise stated, vertical and horizontal coordinate information is referenced to the
World Geodetic System of 1984 (WGS 84). Altitude, as used in this report, refers to distance
above the vertical datum.
Supplemental Information
Specific conductance is given in microsiemens per centimeter at 25 degrees Celsius (µS/cm
at 25 °C).
Concentrations of chemical constituents in soils and (or) sediment are given in milligrams per
kilogram (mg/kg), parts per million (ppm), or parts per billion (ppb).
Concentrations of chemical constituents in water are given in milligrams per liter (mg/L),
micrograms per liter (µg/L), nanogams per liter (ng/L), nanomoles per kilogram (nmol/kg),
parts per million (ppm), parts per billion (ppb), or parts per trillion (ppt).
Concentrations of suspended particulates in water are given in micrograms per gram (µg/g),
milligrams per kilogram (mg/kg), or femtograms per gram (fg/g).
Concentrations of chemicals in air are given in units of the mass of the chemical (milligrams,
micrograms, nanograms, or picograms) per volume of air (cubic meter).
Activities for radioactive constituents in air are given in microcuries per milliliter (μCi/mL).
Deposit grades are commonly given in percent, grams per metric ton (g/t)—which is equivalent
to parts per million (ppm)—or troy ounces per short ton (oz/T).
Geologic ages are expressed in mega-annum (Ma, million years before present, or 10 6 years ago)
or giga-annum (Ga, billion years before present, or 10 9 years ago).
For ranges of years, “to” and (or) the en dash (“–”) mean “up to and including.”
Concentration unit Equals

milligram per kilogram (mg/kg) part per million
microgram per gram (µg/g) part per million
microgram per kilogram (μg/kg) part per billion (109)
Equivalencies
part per million (ppm): 1 ppm = 1,000 ppb = 1,000,000 ppt = 0.0001 percent
part per billion (ppb): 0.001 ppm = 1 ppb = 1,000 ppt = 0.0000001 percent
part per trillion (ppt): 0.000001 ppm = 0.001 ppb = 1 ppt = 0.0000000001 percent
Metric system prefixes

tera- (T-) 1012 1 trillion
giga- (G-) 109 1 billion
mega- (M-) 106 1 million
kilo- (k-) 103 1 thousand
hecto- (h-) 102 1 hundred
deka- (da-) 10 1 ten
deci- (d-) 10–1 1 tenth
centi- (c-) 10–2 1 hundredth
milli- (m-) 10–3 1 thousandth
micro- (µ-) 10–6 1 millionth
nano- (n-) 10–9 1 billionth
pico- (p-) 10–12 1 trillionth
femto- (f-) 10–15 1 quadrillionth
atto- (a-) 10–18 1 quintillionth
viii
Abbreviations and Symbols

°C degree Celsius
µg/L microgram per liter
µg Al/L microgram of aluminum per liter
µg Mn/m3 microgram of manganese per cubic meter
µg Mn/L microgram of manganese per liter
Å angstrom
AMD acid mine drainage
ATSDR Agency for Toxic Substances and Disease Registry
CIGS copper-indium-gallium-(di)selenide
g CO2-equiv/kWh gram of CO2 equivalent per kilowatthour
LC50 lethal concentration 50 (concentration that kills 50 percent of test
population within a given timeframe)
LED light-emitting diode
Ma mega-annum
mg Al/kg milligram of aluminum per kilogram
mg/kg milligram per kilogram
mg/L milligram per liter
mm millimeter
ng/m3 nanogram per cubic meter
OSHA Occupational Safety and Health Administration
ppm part per million
RF radio-frequency
SAF submerged-arc furnace
USGS U.S. Geological Survey
Gallium
By Nora K. Foley, Brian W. Jaskula, Bryn E. Kimball, and Ruth F. Schulte
Abstract imports of primary, recycled, and refined gallium, as well as

through domestic production of recycled and refined gallium.
Gallium is a soft, silvery metallic element with an The U.S. Geological Survey estimates that world resources
atomic number of 31 and the chemical symbol Ga. Gallium is of gallium in bauxite exceed 1 billion kilograms, and a
used in a wide variety of products that have microelectronic considerable quantity of gallium could be present in world
components containing either gallium arsenide (GaAs) or zinc reserves.
gallium nitride (GaN). GaAs is able to change electricity
directly into laser light and is used in the manufacture of
optoelectronic devices (laser diodes, light-emitting diodes Introduction
[LEDs], photo detectors, and solar cells), which are important
for aerospace and telecommunications applications and The existence of gallium was first predicted in 1871 by
industrial and medical equipment. GaAs is also used in Dmitri Mendeleev, a Russian chemist who published the first
the production of highly specialized integrated circuits, periodic table of elements (Mendeleev, 1871). Mendeleev
semiconductors, and transistors; these are necessary for defense noted a gap in his table and named the missing element
applications and high-performance computers. For example, “eka-aluminum” because he determined that its location
cell phones with advanced personal computer-like functionality was one place away from aluminum in the table (fig. H1).
(smartphones) use GaAs-rich semiconductor components. Mendeleev thought that the missing element (gallium) would be
GaN is used principally in the manufacture of LEDs and laser
diodes, power electronics, and radio-frequency electronics.
Because GaN power transistors operate at higher voltages and
with a higher power density than GaAs devices, the uses for
advanced GaN-based products are expected to increase in the
future. Gallium technologies also have large power-handling
capabilities and are used for cable television transmission,
commercial wireless infrastructure, power electronics, and 13 14
satellites. Gallium is also used for such familiar applications Al Si
as screen backlighting for computer notebooks, flat-screen 26.98 28.09
televisions, and desktop computer monitors. 30 31 32

Gallium is dispersed in small amounts in many minerals Zn Ga Ge
and rocks where it substitutes for elements of similar size and 65.39 69.72 72.64
charge, such as aluminum and zinc. For example, gallium 48 49 50

is found in small amounts (about 50 parts per million) in Cd In Sn
112.4 114.8 118.7
such aluminum-bearing minerals as diaspore-boehmite and
gibbsite, which form bauxite deposits, and in the zinc-sulfide
Figure
H1. H1Photograph of gallium metal with an inset showing
mineral sphalerite, which is found in many mineral deposits. Figure
At the present time, gallium metal is derived mainly as a its position on the periodic table of elements. The gallium
byproduct of the processing of bauxite ore for aluminum; crystals shown in the photograph grew in a tank of liquid
lesser amounts of gallium metal are produced from the gallium. The drop in the foreground fell off the crystal as the
processing of sphalerite ore from three types of deposits liquid slowly cooled below a temperature of about 30 degrees
(sediment-hosted, Mississippi Valley-type, and volcanogenic Celsius. Photograph courtesy of Afshin Yaghmaei, Simulated
massive sulfide) for zinc. The United States is expected to Planetary Interiors Lab, Department of Earth and Space
meet its current and expected future needs for gallium through Sciences, University of California, Los Angeles.
H2 Critical Mineral Resources of the United States— Gallium
very much like aluminum in its chemical properties, and he was medical equipment. GaAs is also used in the production of
right. The French chemist Paul-Emile Lecoq de Boisbaudran highly specialized integrated circuits, semiconductors, and
discovered gallium in sphalerite in 1875 using spectroscopy. transistors; these are necessary for defense applications and
Lecoq de Boisbaudran isolated gallium metal by electrolysis high-performance computers. For example, smartphones (cell
of gallium hydroxide in a potassium hydroxide solution. phones with advanced computer-like functionality) use GaAs-
He named the element “gallia” after the Latin name for his rich semiconductor components (fig. H2A). GaN is employed
native land of France (Gallia, or Gaul). principally in the manufacture of LEDs and laser diodes, power
Solid gallium has a low melting temperature (about electronics, and radio-frequency (RF) electronics. Because
29 degrees Celsius [°C]) and an unusually high boiling GaN power transistors operate at higher voltages and with
point (about 2,204 °C) (table H1), so that gallium is a liquid a higher power density than GaAs devices, the applications
across a wider range of temperatures than any other element. for advanced GaN-based products are expected to increase
Because of these properties, the earliest uses of gallium were in the future. The CIGS direct band-gap semiconductor was
in high-temperature thermometry and in metal alloys that developed to make lightweight, flexible, and durable thin-film
melt easily. The development of gallium arsenide as a direct photovoltaics that have a high absorption coefficient; these
band-gap semiconductor in the 1960s led to what are now attributes have potential applications in the manufacture of
some of the most well-known uses of gallium—in feature-rich, efficient solar cells (fig. H2B). Because of its high boiling
application-intensive, third- and fourth-generation smart- temperature, gallium is used to make thermometers designed
phones and in data-centric networks. to measure very high temperatures, and because of its silvery
color and ability to form metal alloys, gallium is used to
make brilliant mirrors. The fundamental properties of thermal
Strategic and Critical Resource Issues convection in liquid gallium metal are employed to study
aspects of planetary and astrophysical magnetohydrodynamics.
Gallium first became recognized as a strategic and critical Gallium can be replaced by other materials in some
metal during World War II because it was a necessary compo- applications, but for others, it has no effective substitutes.
nent of a stable gallium-plutonium alloy that was developed Liquid crystals made from organic compounds are used in
as part of the Manhattan Project and used to make a reliable visual displays as substitutes for LEDs. Researchers also are
atomic bomb. Gallium is currently important for U.S. manu- working to develop organic-based LEDs that may compete
facturing because of its expanding uses for novel thin-film with GaAs in the future. Indium phosphide components can
photovoltaics, especially those of the copper-indium-gallium- be substituted for GaAs-based infrared laser diodes in some
(di)selenide (CIGS) semiconductor type, and it is particularly specific-wavelength applications, and helium-neon lasers
important for clean energy technologies. Gallium is currently can be used in place of GaAs lasers in visible laser diode
produced as a byproduct of the mining of other mineral applications. Silicon is the principal competitor with GaAs
commodities—mainly zinc, copper, and aluminum—and the in solar-cell applications. GaAs-based integrated circuits are
mining technologies used are optimized for the extraction of used in many defense-related applications because of their
those primary mineral commodities. The small market for unique properties, and there are no effective substitutes for
gallium as a specialty metal creates little incentive for refiners GaAs in these applications. GaAs in heterojunction bipolar
of zinc, copper, and aluminum ores to invest in improvements transistors is being substituted by silicon-germanium in
to increase byproduct recovery of gallium. Because of the some applications.
likelihood of rapid growth in the areas of photovoltaics and In 2012, imports of gallium and GaAs wafers, which
clean energy technologies, a potential exists for bottlenecks in were valued at about $32 million, continued to satisfy almost
the gallium supply pipeline. Production of gallium is limited all U.S. demand for gallium. GaAs and GaN electronic
by market factors that influence the production of the principal components represented about 99 percent of domestic gallium
mineral commodity, whether it is zinc or aluminum. consumption (fig. H3). About 70 percent of the gallium was
used in integrated circuits (both analog and digital), including
those in defense applications, high-performance computers,
Uses and Applications and telecommunications. Optoelectronic devices for use in
aerospace and telecommunications applications, consumer
A wide variety of products have microelectronic compo- goods, industrial equipment, medical equipment, and so forth,
nents that contain either gallium arsenide (GaAs) or gallium as well as a small amount for research and development,
nitride (GaN). GaAs is able to change electricity directly into represented the remaining 30 percent of gallium consumption.
laser light and is used in the manufacture of optoelectronic Gallium prices decreased throughout 2012 when
devices (laser diodes, light-emitting diodes [LEDs], photo significant increases in gallium production from 2007
detectors, and solar cells), which are important for aerospace to 2012 (fig. H4) exceeded the declining demand from
and telecommunications applications and industrial and LED producers. Gallium production capacity in China
Introduction H3
expanded tremendously from 2008 to 2012 on the expectation oversupply of CIGS modules that caused prices to decrease
of a strong LED-based backlighting market, which failed to by 20 percent in 2011 and to remain low throughout 2012. In
materialize. In January 2012, the price for low-grade gallium an effort to keep CIGS technology viable and competitive,
metal (with a purity of 99.099 percent compared with a purity CIGS manufacturers began in 2011 to trim production costs,
of 99.99999 for the higher grade) averaged $580 per kilogram. improve module conversion efficiencies, and increase the use
By July, the average price for low-grade gallium metal had of CIGS-based photovoltaics in commercial rooftops.
decreased to $320 per kilogram, and by early October, to The following sections of this chapter provide an over-
$280 per kilogram. view of the principal types and global distribution of domestic
Markets continued to expand for GaAs- and GaN-based and global resources of gallium (fig. H4). This information
products in 2012. GaAs demand mainly results from cell updates the report by Weeks (1973).
phones and other high-speed wireless applications. In 2012,
GaAs demand increased owing to the rapid increase in the
use of feature-rich, application-intensive, third- and fourth- A
generation smartphones, which contain up to 10 times the
amount of GaAs compared with standard cellular handsets.
Smartphones accounted for 37 percent of all handsets sold
in 2012. Owing to the increased amounts of GaAs in smart-
phones and the increased use of GaAs-based LEDs in general
lighting and automotive applications, the value of sales in the
GaAs market is forecast to reach $650 million by 2017 at an
annual growth rate of nearly 11 percent (Jaskula, 2013b).
Owing to the large power-handling capabilities, high-
switching frequencies, and higher voltage capabilities of
GaN technology, GaN-based products, which historically
have been used in defense and military applications, have
begun to gain acceptance in the cable television transmission,
commercial wireless infrastructure, power electronics, and
satellite markets. The value of sales for the GaN power device B
market was expected to reach $178 million by 2015 at an
annual growth rate of nearly 29 percent (Jaskula, 2013b).
In 2012, the worldwide LED market, which was a
significant driver for GaN-based technologies, increased
by only 1.5 percent in revenues from that of 2011 owing
to slower-than-expected growth in the LED backlighting
market and to lower LED prices, as production was outpacing
demand. Although televisions were increasingly being built
with LED backlighting in 2012, improvements in technology
required up to 50 percent fewer LEDs. LED-backlit televisions
accounted for 63 percent of the television market in 2012
and were forecast to account for 93 percent of market sales GalliumH2.
Figure Figure 3.
Photographs showing examples of some current
in 2013. By 2014, the strongest market segments for sales of uses for gallium. A, Cell phone that has advanced computer-like
LEDs were expected to be in general lighting, followed by functionality (that is, a smartphone), which contains gallium-
signs and automotive applications. based semiconductor components and, consequently, up to
Sustained high prices for energy continued to spark 10 times the amount of gallium arsenide (GaAs) than is used in
interest in solar energy in 2012. Sales of CIGS semiconductors standard cell phones. B, Experimental three-wheel car displaying
for use in the production of high-efficiency solar cells was high-efficiency, triple-junction GaAs solar cells. Such solar cells
slower than expected, however, owing to a complicated have many experimental applications; this three-wheel car, the
manufacturing process that has impeded commercial mass Continuum, which was built at the University of Michigan, weighs
production of CIGS panels. Decreased prices of silicon-based 220 kilograms and is covered with about 2,500 aerospace-grade
solar cells also affected demand for the more expensive GaAs-type solar cells. Photograph of experimental car courtesy
CIGS technology. These two factors resulted in a large of the University of Michigan.
A. Estimated world primary gallium production

400
EXPLANATION
Gallium content, in metric tons
Primary production Refined production (includes

300 Primary gallium primary production until 2011)
producers: Refined gallium producers:
China China
200 Germany Japan
Hungary United Kingdom
Japan United States
100 Kazakhstan
Republic of Korea
Russia
Ukraine
0
2007 2008 2009 2010 2011 2012
B. Estimated world primary gallium production capacity

400
China Other producers

300
200
100
No
estimate
0
2007 2008 2009 2010 2011 2012
C. U.S. gallium consumption U.S. gallium consumption by end use, 2012

100
Solar cells
80 2%
Digital Research and
integrated circuits development
60 8% < 0.5%
LEDs and
40
laser diodes Analog
30% integrated
20
circuits
60%
0
2007 2008 2009 2010 2011 2012
Year
Figure H3. Charts showing U.S. and world gallium production and consumption from 2007 to 2012. A, Estimated world
primary gallium production and refined gallium production from 2007 to 2012. B, Estimated world primary gallium production
capacity forGallium Figure
China and 4 of the world from 2008 to 2012. C, Gallium consumption in the United States from 2007 to 2012,
the rest
and major end uses of gallium as a percentage of U.S. consumption in 2012. Percentages in the pie chart have been rounded
and consequently do not add to 100. LEDs, light-emitting diodes
AU: The text mentions Mount Isa, and the Cooley and Ridge Mines as being
Kipushi-type deposits also, but they are not shown on this map?
180° 135° 90° 45° 0° 45° 90° 135° 180°

80°
70° Red Dog Nanisivik

Southern
European
Ruby Creek Russian province
60° province
50° Upper
Mississippi
Valley
40° Viburnum Trend
Apex
Austinville Chinese
province
30° Arkansas
province Caribbean
province
20°
Indian
Guyana Shield province
10°
province
Guinea Shield
0°
province Cameroon
province
10°
Brazilian Shield Kipushi
province
20°
EXPLANATION
Gallium sources Australian province
30°
Bauxite deposits
Sediment-hosted
40° zinc deposits
Kipushi-type deposits
50°
60°
70°
80°
Base from U.S. Geological Survey Global 30 arc-second elevation data (1996) and from Natural Earth (2014); Robinson projection; World Geodetic System 1984 datum
Figure H4. World map showing

Galliumlocations
figureof1.selected mineral deposits, by type; gallium has been produced from these types of deposits. The selected bauxite deposits are
located within the world’s major bauxite provinces and include both karst and lateritic types. The sediment-hosted zinc deposits and districts named in the text (Austinville,
Nanisivik, Red Dog, Ruby Creek, and Viburnum Trend) are labeled. (See Taylor and others [2009] for names and details regarding other zinc deposits.) Not all the Kipushi-type
deposits mentioned in the text appear on this map.
Introduction H5
Geology Pearson hard acids (Pearson, 1963), which favor the formation
of complexes with hard ligands, such as fluoride, hydroxide,
Gallium occurs in low amounts in a diverse group of phosphate, and sulfate. In aqueous solutions, gallium is
geologic environments and is found most commonly in asso- predicted to occur mainly in fluoride and hydroxide complexes
ciation with deposits of aluminum and zinc (fig. H5), which (Wood and Samson, 2006). Solubility products of most
are its immediate neighbors in the periodic table of elements solid phases containing gallium are generally not available;
(fig. H1). The average abundance of gallium in Earth’s crust however, the limited available solubility data constrain the
is generally less than 19 parts per million (ppm) (table H2). maximum concentrations of gallium to be expected in aqueous
Because of the rarity of gallium in most geologic environ- fluids to the subparts-per-million to subparts-per-billion (or
ments, minerals containing gallium as an essential structural micrograms per liter) range (Wood and Samson, 2006), and
component are also rare (table H3). Because gallium occurs this is evident in the values seen for hydrothermal fluids,
as a minor or trace element in many minerals, there are a large river waters, and seawater (table H2). The hydrolysis of
number of rock types and tectonic settings for mineral deposits GaOOH(s) (solid gallium oxyhydroxide) occurs at low pH,
that are known to contain gallium in potentially extractable and its speciation is strongly dominated by Ga(OH)4– in the pH
amounts (table H4). At the present time, the majority of the range of natural solutions at 25 °C. At increasing temperature,
world’s supply of newly mined gallium metal comes from the amount of Ga(OH)2+ and Ga(OH)3° becomes significant,
bauxite and sediment-hosted lead-zinc deposits (fig. H4). although at 300 °C, Ga(OH)4– remains the predominant
Gallium is currently derived as a byproduct of the processing species. A comparison of the geochemical behavior of gallium
of bauxite ore for aluminum, with lesser amounts produced and aluminum in natural fluids indicates that Ga(OH)4–
from residues resulting from the processing of sphalerite ore exhibits a chemical behavior very similar to that of Al(OH)4−
for zinc. (Wood and Samson, 2006). The low solubility of α-GaOOH(s)
(in the absence of fluoride or strong organic ligands at low
temperatures) is consistent with the immobility of gallium
Geochemistry relative to most other elements, except aluminum, during
weathering and alteration processes. This immobility leads
Gallium is a soft, silvery post-transition metal with an to the accumulation of gallium in some bauxites and kaolins,
atomic number of 31 (table H1; fig. H1) that is very much and in the high-alumina hydrothermal alteration halos that
like aluminum in its chemical properties. The chemical form around many mineral deposits (for example, epithermal,
similarities between gallium and aluminum, which include a porphyry, and volcanogenic deposits).
trivalent oxidation state, a similar atomic radius, tetrahedral
or octahedral coordination in minerals, and amphoterism
(that is, they can act as both acid and base in reactions),
result in their generally synchronous geochemical behavior.
Gallium is found primarily in the trivalent oxidation state;
mixed-oxidation state compounds containing both Ga1+ and
Ga3+ (ionic radius of about 0.62 angstrom [Å]) occur but are Figure H5. (page H7) Cross sections showing the general
not common (Eagleson, 1994, p. 438). In compounds, gallium geologic environments for the types of mineral deposits with
exhibits a chemical similarity to Al3+ (ionic radius of about which gallium is most commonly associated and from which
0.54 Å), Fe3+ (ionic radius of about 0.69 Å) and Zn2+ (ionic gallium is typically extracted. A, Karst bauxite deposits, which
radius of about 0.72 Å) (Shannon, 1976) and can substitute form by deep weathering and transport of material in carbonate
for these elements in the common rock-forming minerals rock-dominated sequences; unlabeled patterns show detritus.
(Burton and Culkin, 1978). Other elements typically found B, Lateritic bauxite deposits, which form mainly by deep
in geochemical association with gallium include cadmium, weathering of material in silicate rock-dominated sequences.
indium, germanium, silicon, and tin (fig. H1). Under certain A and B modified from Retallack (2010). C, Sediment-hosted
geochemical conditions, these elements can be separated in lead-zinc deposits, which form in passive margin environments.
near-surface environments—for example, by changes in pH D, Clastic-dominated-type lead-zinc deposits, which may form by
or redox conditions—because their acid/base and electronic brine reflux in shales and deep-water carbonates. E, Mississippi
properties are sufficiently different (table H1). Valley-type lead-zinc deposits, which form by replacement in
The aqueous geochemistry of gallium was studied by platform carbonate sequences. C, D, and E modified from Kelley
Wood and Samson (2006, and references therein) based on a and others (1995); Bradley and Leach (2003); Leach, Sangster,
number of earlier works. Trivalent gallium is also the most and others (2005); and Leach, Taylor, and others (2010).
common oxidation state of gallium metal in aqueous solution
and, owing to the high charge, the hydrated ions of gallium are
Geology H7
A. Karst bauxite deposits B. Lateritic bauxite deposits

Soil
Soil
Lateritic paleosol
Younger limestone bauxite
Lateritic
cuirasse
Bauxitic paleosol
Saprolite
Bauxite
Bauxitic pedolith pallid zone
Mottled zone
Bauxitic paleosol Lateritic

pedolith
Bauxitic pedolith
Bedrock
Bedrock
C. Sediment-hosted lead-zinc deposits D. Clastic-dominated-type lead-zinc deposits

Sea level Reflux model for passive continental margin
Clastic-dominated
type host Open marine environment Evaporative basin
environment Brine pool Brine discharge Brine generation
Mississippi Valley-
type host Dolomitization
environment Brine influx
Underlying rocks Metal extraction
EXPLANATION (part C ) EXPLANATION (part D )

Mafic and ultramafic rocks Shale, deep-water carbonates Carbonate rocks
Carbonate and minor Rift facies rocks Clastic rocks—Massive (solid pattern) and
clastic rocks of the Basement rocks laminated (striped pattern)
passive margin platform Lead-zinc ores in clastic rocks
Carbonate turbidites
Fault
E. Mississippi Valley-type lead-zinc deposits
Central Viburnum Northern

Tri-State
Missouri North End Arkansas Surface gradient towards craton
Filled basins
EXPLANATION
Graywacke turbidites, molasse facies rocks
Shale, deep-water carbonates
Carbonate and minor clastic rocks of the
passive margin platform
Precambrian basement rocks
Fault Location of ore
ALL FIGURES NOT TO SCALE
Gallium Figure 5
Table H1. Selected properties of gallium, a Group 13 post- higher ranges, from 20 to 70 ppm gallium (Burton and Culkin,
transition metal. 1978). Values of gallium in shale, sandstone, and carbonates
are 19 ppm, 12 ppm, and 4 ppm, respectively (Mielke, 1979),
[Sources: Instytutu Problem Materialoznavstva (1968) and Lide (2005,
and gallium in loess averages about 14 ppm (McLennan and
p. 14–39). Å, angstrom; °C, degree Celsius; cm, centimeter; eV, electron-
volt; g/cm3, gram per cubic centimeter; GPa, gigapascal; J/mol-K, joule per Murray, 1999).
mole kelvin; K, kelvin; kJ/mol, kilojoule per mole; nΩ-m, nano ohm-meter; Gallium contents of rocks may be increased by greiseni-
μm/m-K, micrometer per meter kelvin; W/m-K, watt per meter kelvin] zation, albitization, hydrothermal alteration, and weathering
processes, including saprolitization and lateritization. In
Property Description general, the bulk content of gallium in a given rock type
Symbol Ga corresponds to the composition and bulk content of feldspar
Atomic number 31
and mica in the rock. Alteration processes that selectively
remove mobile elements from aluminosilicate minerals
Atomic weight 69.723 result in relative increases in the concentrations of gallium,
Isotopes 24 radioisotopes; 69Ga, 71Ga aluminum, and other less mobile elements in all rock types.
are stable isotopes; 67Ga has The chalcophile behavior of gallium contributes to its
a half-life of about 3.3 days concentration in sulfide ores, which can contain hundreds
of parts per million gallium (Burton and Culkin, 1978). In
Density at 293 K (g/cm3) 5.91
hydrothermal systems related to sulfide mineralization and in
Melting point (°C) 29.7646 residual deposits formed by surficial weathering, the lithophile
Boiling point (°C) 2,204 and chalcophile tendencies of gallium work in opposition in
Heat of fusion (kJ/mol) 5.59
terms of enrichment, as sulfide and aluminosilicate minerals
compete for gallium.
Heat of vaporization (kJ/mol) 254 The value of the ratio of aluminum to gallium (the
Molar heat capacity (J/mol-K) 25.86 Al:Ga ratio) has been used as an indicator of gallium enrich-
Hardness (Mohs scale) 1.5 ment because it is thought to be relatively constant in most
types of crustal rocks (Burton and Culkin, 1978). The value
Brinell hardness (GPa) 0.06
of the Al:Ga ratio in various common rock types can range
Electrical resistivity at 20 °C 270 from 5,000 to 40,000. It is lower, in the range of 1,000 to
(nΩ-m) 10,000, in alkaline igneous rocks and in sedimentary rocks
Thermal conductivity (W/m-K) 40.6 produced by intense weathering (Burton and Culkin, 1978;
Thermal expansion at 25 °C 18 Tervek and Fay, 1986). Rytuba and others (2003) evaluated the
(µm/m-K) geochemical behavior of gallium in igneous rocks using the
Young’s modulus (GPa) 9.8
worldwide GEOROC (Geochemistry of Rocks of the Oceans
and Continents) database (Max Planck Institute, 2002). They
Crystal structure Orthorhombic found that volcanic rocks from convergent-margin environ-
Magnetic ordering Diamagnetic ments with about 8 to 30 ppm gallium had values of Al:Ga that
Electron configuration [Ar] 4s2 3d10 4p1 increased from about 3,000 to 8,000 with increasing aluminum
content. They concluded that gallium is not enriched by
Ionic radius (Å) 0.62
petrologic processes in more evolved silicic volcanic rocks,
First ionization potential (eV) 5.999 such as peralkaline rocks, because the Al:Ga ratio did not
Second ionization potential (eV) 20.51 correlate with increasing quartz (SiO2 ) content or alkalinity.
Third ionization potential (eV) 30.71 A comparison of the data for volcanic rocks worldwide, hydro-
thermally altered rocks of the McDermitt caldera near the
Common valance states Primarily +3, also +2, +1
McDermitt Mine in Humboldt County, Nevada (from Rytuba
and others, 2003), and globally distributed bauxite deposits
shows that gallium concentration is higher in rocks that have
Gallium is the 34th most abundant element found in lower ratios of Al:Ga owing to hydrothermal alteration and
Earth’s crust (Emsley, 2001), and it is widely distributed in (or) intense weathering (fig. H6). Because the Al:Ga ratio can
low amounts in many rock types (table H2). The average be quite variable in natural waters (table H2) owing to differ-
values for gallium in igneous rocks vary considerably, from ences in the mobility of gallium and aluminum in aqueous
a low of about 5 ppm gallium or less in ultramafic rocks to a solutions, the Al:Ga ratio has been used effectively to model
range of 10 to 22 ppm for most mafic to intermediate rocks, the behavior of trace metals as a result of surficial weathering
and to about 16 to 35 ppm gallium for granitic rocks (Burton processes (Hieronymus and others, 1990; Shiller and Frilot,
and Culkin, 1978). Alkaline rocks, particularly nepheline 1996) and in ocean waters (Orians and Bruland, 1988; Shiller,
syenites, granites, and related pegmatites, have generally 1998) and river waters (Shiller, 1998; Shiller and Frilot, 1996).
Geology H9
Table H2. Gallium concentrations in rocks, ore, coal, soils, and natural waters.— Continued
[FOREGS, Forum of European Geological Surveys, now EuroGeoSurveys; Ga, gallium; ICP-MS, inductively coupled plasma-mass spectrometry; XRF,
X-ray fluorescence. Units of measure: cm, centimeter; m, meter; mm, millimeter; ppb, part per billion; ppm, part per million; µg/L, microgram per liter;
µm, micrometer. —, no data]
Gallium concentration
Environment (value or range) Unit Type Notes Reference(s)
and (or) location
Typical Average
Rocks
Upper continental crust — 17, 17.5 ppm Continental crust Average Taylor and McLennan
(1995); Rudnick and
Gao (2003)
Bulk continental crust — 18 ppm Continental crust Average Taylor and McLennan
(1995)
Lower continental — 18 ppm Continental crust Average Taylor and McLennan
crust (1995)
Volcanic rocks — About 8 to 30 ppm Convergent 2,929 analyses Rytuba and others (2003)
margins
High-sulfidation — Up to 320 ppm Alteration None Melfos and Voudouris
epithermal (2012)
High-sulfidation <9 to 38 ppm Alteration None Khashgerel and others
epithermal (2008)
All types 8 to 812 41 ppm Bauxite None Schulte and Foley (2014)
Arkansas (lateritic — 86 ppm Bauxite None Burton and Culkin (1978)
bauxite)
Bosnia — 46 ppm Bauxite None Schulte and Foley (2014)
France — 63 ppm Bauxite None Schulte and Foley (2014)
India 5 to 122 60 ppm Bauxite None Burton and Culkin (1978)
Karst 10 to 812 41 ppm Bauxite None Schulte and Foley (2014)
Lateritic 8 to 136 56 ppm Bauxite None Schulte and Foley (2014)
Malaysia 22 to 47 33 ppm Bauxite None Burton and Culkin (1978)
Russia 10 to 170 54 ppm Bauxite None Burton and Culkin (1978)
Turkey — 68 ppm Bauxite None Schulte and Foley (2014)
Indiana—Danville 1.7 to 8.9 5.06 ppm Coal Pennsylvanian Mastalerz and Drobniak
member (2012)
Indiana—Springfield 1.4 to 12.3 3.39 ppm Coal Pennsylvanian Mastalerz and Drobniak
member (2012)
USGS COALQUAL About 3 to 7 — ppm Selected domestic Averages Finkelman (1993)
database coal-bearing
regions, averages
General <6 to 66 ppm Kaolin None Hieronymus and others
(1990)
Georgia 27 to 100 — ppm Kaolin None This study; Bárdossy (1982);
Bárdossy and Aleva (1990)
Haile kaolin deposit, <6 to 31 19 ppm Kaolin None This study
South Carolina
Malaysia 20 to 25 23 ppm Kaolin None Burton and Culkin (1978)
Geothermal fields 8 to 144 — ppm Muds and sinter None Crump (1994)
and (or) location
Typical Average
Rocks—Continued
Alkaline — About 20 to 70 ppm Rock None Burton and Culkin (1978)
Carbonate rock — 4 ppm Rock Average Mielke (1979)
Granitic — About 16 to 35 ppm Rock None Burton and Culkin (1978)
Loess — 14 ppm Rock Average McLennan and Murray
(1999)
Mafic to intermediate — About 10 to 22 ppm Rock None Burton and Culkin (1978)
Peralkaline — About 28 to 39 ppm Rock None MacDonald and Bailey
(1973)
Shale — 19 ppm Rock Average Mielke (1979)
Sandstone — 12 ppm Rock Average Mielke (1979)
Ultramafic — About 5 ppm Rock None Burton and Culkin (1978)
Apex Mine, Utah 320 to 1,480 — ppm Sulfide None Bernstein (1986)
Ruby Creek Mine, — <<1 ppm Sulfide None Bernstein and Cox (1986)
Alaska
Cadmium-lead-zinc <1 to 1,600 60 ppm Sulfide None Schulte and Foley (2014)
ore, general
Kipushi ore, general <1 to 2,500 10s to 100s ppm Sulfide None Schulte and Foley (2014)
Mississippi Valley- <1 to 500 57 ppm Sulfide None Schulte and Foley (2014)
type ore, general
Sulfide ore, bulk 20 to 1,000 100? ppm Sulfide None Burton and Culkin (1978)
Callahan Mine, Maine — 25 ppm Volcanogenic None Ayuso and others (2013)
massive sulfide,
bulk sulfide
Red Dog Mine, — 26 ppm Clastic-dominated, None Alaska Department
Alaska ore concentrate of Environmental
Conservation (2005)
Soils
World — 17 ppm Soil, bulk None Koljonen (1992)
Western United States — 16 ppm Soil Mean for 20 cm Shacklette and Boerngen
depth (1984)
Eastern United States — 9.3 ppm Soil Mean for 20 cm Shacklette and Boerngen
depth (1984)
Poland — 100 ± 5 ppm Soil Agricultural Połedniok and others (2012)
Poland — 93 ± 7 ppm Soil, proximal Proximal to Połedniok and others (2012)
to a former a former
Zn-Pb mine Zn-Pb mine
Poland — 268 ± 19 ppm Soil, proximal to Proximal to Połedniok and others (2012)
Zn-Pb ore and a Zn-Pb ore and a
bauxite mine bauxite mine
Sweden — 7 to 13 ppm Soil developed Profile range Tyler (2004)
on quartzite
and gneiss
Geology H11
and (or) location
Typical Average
Soils—Continued
FOREGS samples, — 0.9 ppm Humus, median < 2.0 mm fraction, Salminen (2015)
median concentration concentration n=367, Total
(ICP-MS)
FOREGS samples, — 13.5 ppm Topsoil < 2.0 mm fraction, Salminen (2015)
median concentration n=843, Total
(ICP-MS)
FOREGS samples, — 13.8 ppm Subsoil < 2.0 mm fraction, Salminen (2015)
median concentration n=790, Total
(ICP-MS)
Waters
Atlantic Ocean — 0.0003 to 0.004 µg/L Seawater Dissolved and col- Shiller (1998)
loidal (<0.4 µm);
surface to 5,000 m
deep
African rivers — 0.02 to 0.11 µg/L River Dissolved load Gaillardet and others
(<0.2 µm) (2003)
North American rivers — 0.001 to 0.012 µg/L River Dissolved load Gaillardet and others
(<0.2 µm) (2003)
South American rivers — 0.003 to 0.12 µg/L River Dissolved load Gaillardet and others
(<0.2 µm) (2003)
California streams — 0.0001 to 0.006 µg/L River Dissolved and colloi- Shiller and Frilot (1996)
dal load (<0.4 µm)
Idel River — 0.009 µg/L River Dissolved load Gaillardet and others
(<0.2 µm) (2003)
Japan — 2.5 ppb Geothermal None Uzumasa and Nasu (1960)
Wairakei, New Zealand — About 0.2 ppb Geothermal None Goguel (1988)
Broadlands, New — About 0.2 ppb Geothermal None Goguel (1988)
Zealand,
Bath, United Kingdom — 0.63 ppb Geothermal None Riley (1961)
Taiwan — 0.01 to >10.00 µg/L Groundwater None Chen (2006)
World rivers 18.1 — ppm Suspended Average Viers and others (2009)
sediment
FOREGS samples, — 0.011 µg/L Water Filtered < 0.45 micro- Salminen (2015)
median concentration meter fraction
FOREGS samples, — 12.0 ppm Stream < 2.0 mm fraction, Salminen (2015)
median concentration sediment n=852, Total (XRF)
FOREGS samples, — 11.0 ppm Flood plain < 2.0 mm fraction, Salminen, 2015
median concentration sediment n=747, Total (XRF)
Mineralogy Namibia (Frimmel and others, 1996, and references therein).

Gallite occurs as a primary sulfide mineral and is essentially
Gallium is an essential structural component of only a common copper sulfide, chalcopyrite (CuFeS2), in which
a few minerals that form in nature. Gallium is dispersed, gallium replaces iron in the crystal structure. Typical occur-
however, in low amounts in many minerals and rocks, rences of gallite are as inclusions in sphalerite (ZnS). Because
where it substitutes for elements of similar size and charge gallite has a chalcopyrite structure, it may occur as either
(table H3). Because gallium minerals are too rare in nature to epitaxial overgrowths or inclusions as “chalcopyrite disease”
serve as a primary source of the element or its compounds, (Barton and Bethke, 1987) in sphalerite. Gallobeudantite,
most gallium is produced from minerals containing less than sohngeite, and tsumgallite are supergene minerals resulting
100 ppm gallium (table H3), where the gallium may occur as from surficial oxidation of other gallium-bearing minerals.
inclusions, as stoichiometric or nonstoichiometric substitu- Gallium also substitutes in many minerals, including silicates,
tions, or as adsorbed ions or molecules. sulfides, and hydroxides, in concentrations ranging from
Four gallium-rich minerals have been recognized parts per million to weight percent (table H3). For example,
(approved) by the International Mineralogical Association, significant amounts occur in krieselite (about 20 weight
Commission on New Minerals, Nomenclature and percent gallium), which is the germanium analog of topaz, and
Classification (table H3). These include the sulfide gallite, in gallium-rich plumbogummite, where it may fill one-third
which has about 35 weight percent gallium; gallobeudantite, of the aluminum sites (about 25 weight percent gallium).
which is an alunite of variable gallium content; and the Major rock-forming minerals, however, contain significantly
hydroxide minerals sohngeite and tsumgallite, both of which less than 1 percent gallium, and most minerals have less
contain about 60 weight percent gallium. These minerals have than 100 ppm gallium. Feldspars and micas are the dominant
been identified in association with carbonate-hosted copper- host minerals for gallium in most igneous and sedimentary
lead-zinc deposits at the Tsumeb Mine in the Oshikoto Region, rocks. For example, gallium has been reported at relatively
30,000
20,000
y= –3,580Ln(x)+15,300 EXPLANATION
10,000 R2 =0.53
Bauxite deposits—15 to 90 ppm gallium
Normal range Worldwide volcanic rocks
of Al:Ga ratios in (n=2,928)
volcanic rocks is
3,000 to 8,000
McDermitt Mine
<30 ppm gallium
Al:Ga ratio
≥30 ppm gallium

y= –1,200Ln(x) +5,800
R2 = 0.16
1,000
y = –1,200Ln(x)+6,100
R2 =0.40
100
1 10 30 100
Ga content, in parts per million
H6. Plot
Figure figure
Gallium 6 of the ratio of aluminum to gallium (Al:Ga, log scale) versus gallium content (in parts per
million [ppm], log scale) for bauxite deposits, volcanic rocks, and hydrothermally altered rocks of the McDermitt
caldera, Nevada. Results from the McDermitt Mine, Nev., are included for comparison; see text for details.
Equations define slope of lines drawn through datasets for comparison; R2 value is a measure of goodness of
the fit of the line to the data. Modified from Rytuba and others (2003) with the addition of data for various globally
distributed bauxite deposits from Schulte and Foley (2014).
Geology H13
Table H3. Selected gallium-bearing minerals—Formula, content, and occurrence.

[Compiled from Burton and Culkin (1978), Bernstein (1986), Dutrizac and others (1986), Tervek and Fay (1986), Frimmel and others (1996), Schlüter and
others (2003), Ye and others (2011), and Schulte and Foley (2014). b.d.l., below detection limit; ppm, part per million; ~, approximately. Elements: Al, aluminum;
Cu, copper; Fe, iron; Ga, gallium; Pb, lead; Zn, zinc]
Mineral name Chemical formula Ga content Group Deposit model, occurrence type
Minerals with essential gallium1 (weight percent)
Gallite CuGaS2 35.32 Sulfide Carbonate-hosted Cu-Pb-Zn; Pb-Zn-Cu
Tsumeb Mine in Namibia
Gallobeudantite PbGa3[(AsO4),(SO4)]2(OH)6 14.55, variable Alunite Carbonate-hosted Cu-Pb-Zn; supergene,
Sohngeite Ga(OH)3 57.74 Hydroxide Carbonate-hosted Cu-Pb-Zn; supergene,
Tsumeb Mine in Namibia.
Tsumgallite GaO(OH) 59.93 Hydroxide Carbonate-hosted Cu-Pb-Zn; supergene,
Minerals with nonessential gallium
Krieselite (Al,Ga)2(GeO4)(OH)2 20.3 weight percent Topaz group, Ge analog of topaz
germanate
Sphalerite ZnS b.d.l. to 2,500 ppm Sulfide Volcanogenic massive sulfide, sedimentary
exhalative, and Mississippi Valley-type
base-metal deposits
Eyselite FeGe3O7(OH) 6,900 ppm Hydroxide Carbonate-hosted Cu-Pb-Zn; Pb-Zn-Cu
Ovamboite Cu20(Fe,Cu,Zn)6W2Ge6S32 4,600 ppm Sulfide, germanite Massive sulfide base-metal ores
group
Calvertite Cu5Ge0.5S4 3,500 ppm Sulfide Carbonate-hosted Cu-Pb-Zn; Pb-Zn-Cu
Ferrohogbomite- (Fe,Zn,Mg,Al)6Al14(Ti,Fe)2 1,600 ppm Oxide High grade Fe-oxide deposits
2N2S O30(OH)2
Maikainite Cu20(Fe,Cu)6Mo2Ge6S32 1,500 ppm Sulfide, germanite Volcanogenic massive sulfide, sedimentary
group exhalative, and Mississippi Valley-type
base-metal deposits. (1) Maikain deposit,
Kazakhstan, and (2) Tsumeb deposit,
Namibia
Plumbogummite, PbH(Al,Ga)3(PO4)2(OH)6 ~25 weight percent Crandallite sub- Carbonate-hosted Cu-Pb-Zn; Pb-Zn-Cu
Ga-rich group, alunite Tsumeb Mine in Namibia
supergroup
Gibbsite Al(OH)3 About 50 ppm Oxide, hydroxide Bauxite-silicate; bauxite-karst
Diaspore α-AlO(OH) About 50 ppm Oxide, hydroxide Bauxite-silicate; bauxite-karst
Boehmite γ-AlO(OH) About 50 ppm Oxide, hydroxide Bauxite-silicate; bauxite-karst
Kaolinite Al2Si2O5(OH)4 About 50 to 200 ppm Silicate Kaolins; bauxite-silicate; bauxite-karst
Halloysite Al2Si2O5(OH)4 About 50 to 200 ppm Silicate Kaolins; bauxite-silicate; bauxite-karst
Jarosite KFe(SO4)2(OH)6 0.7 weight percent Sulfite Supergene
Limonite FeO(OH) • nH2O 2 weight percent Hydroxide Supergene
Goethite FeO(OH) 200 ppm Hydroxide Supergene
Renierite (Cu,Zn)11(Ge,As)2Fe4S16 0.04 to 400 ppm Sulfide, germanite Massive sulfide base-metal ores
group
Germanite Cu26Fe4Ge4S32 0.09 to 900 ppm Sulfide, germanite Massive sulfide base-metal ores
group
Feldspar group NaAlSi3O8, CaAl2Si2O8, b.d.l. to 100 ppm, rarely Silicate Felsic igneous rocks
KAlSi3O8 up to 4,000 ppm
1
Approved by the International Mineralogical Association, Commission on New Minerals, Nomenclature and Classification.
high concentrations (0.05 weight percent) in feldspars from Gibbsite-Diaspore-Boehmite

the Nechalacho layered nepheline-aegirine syenite suite at
Thor Lake in the Northwest Territories, Canada (Tervek Gibbsite forms in weathering environments by a series
and Fay, 1986); however, most feldspar contains much less of reactions generated during the hydrolysis of feldspar and
than 200 ppm gallium (table H3). Gallium is retained in clay other aluminosilicate minerals in rocks undergoing saproliti
minerals, such as kaolinite and smectite, and in aluminum zation (Foley and Ayuso, 2013, and references therein). The
hydroxide minerals during weathering, which accounts for proportion of gibbsite-diaspore-boehmite increases at the
the higher gallium contents in many clay-bearing rocks and expense of kaolinite in more intensely weathered rocks, such
bauxites (table H2). At the present time, gallium is derived as bauxites and laterites (Soler and Lasaga, 1996). In these
mainly from aluminum hydroxide minerals, including environments, as a result of burial diagenesis or low-grade
boehmite, diaspore, and gibbsite (Al(OH)3), which form in regional metamorphism, gibbsite transforms to boehmite
deeply weathered deposits of bauxite (fig. H7A) (Dutrizac (γ-AlO(OH)) by dehydration, and turns into diaspore
and others, 1986; Bernstein and Waychunas, 1987; Moskalyk, (α-AlO(OH)) after compaction. Gallium in these minerals
2003). Significant amounts of gallium are also produced from may be found as substitutions for trivalent aluminum or it
zinc sulfide deposits where sphalerite (fig. H7B) is the main may form as a separate phase (table H3). Sohngeite, which
carrier (Moskalyk, 2003). Gallium (and germanium) can is the gallium analog of gibbsite, has a similar stability, and
also be enriched in other sulfide minerals, such as bornite, it transforms readily into tsumgallite (GaO(OH)) in aqueous
enargite, galena, and luzonite (Hörmann, 1978). Weathering of solution (table H3). The unit cell parameters of tsumgallite
gallium-bearing sulfide minerals can lead to gallium-enriched mostly resemble diaspore compared with gibbsite or boehmite
sulfate and hydroxide minerals, and in oxidized environ- (Schlüter and others, 2003). Gallium hydroxide minerals
ments, gallium commonly occurs in plumbojarosite and rarely form as discrete phases; rather, they generally occur in
hydrogoethite (Burton and Culkin, 1978). At the Apex Mine supergene parts of carbonate-hosted polymetallic replacement
in Summit County, Utah, jarosite (a potassium-iron-sulfate deposits, such as at the Tsumeb Mine in Namibia (Frimmel
mineral) reportedly contains concentrations of up to 1 weight and others, 1996). Diaspore and tsumgallite are isostructural,
percent gallium (Bernstein, 1986). have similar crystal chemical characteristics, and are the most
A B
Gallium
Figure Figure
H7. 7.
Photographs showing samples of A, bauxite ore, and B, sphalerite ore, which are the primary
mineralogical sources of gallium. The three samples of bauxite are from U.S. Geological Survey (USGS) collections
and the powdered bauxite ore sample was provided by E.L. Bray, USGS. The sphalerite ore is from the Creede district,
San Juan County, Colorado.
Geology H15
stable hydroxides of aluminum and gallium, respectively. is produced mainly as a byproduct. More than 80 percent of
Thus, gallium, in the form of GaO(OH), is more likely to be the world’s refined gallium is obtained from bauxite deposits
enriched in diaspore than in the other aluminum hydroxides. (Jaskula, 2013b). The balance is derived from operations that
collect zinc residues from a variety of zinc deposit types;
the residues are combined prior to the gallium extraction
Sphalerite
cycle. Among zinc deposits, gallium concentrations tend
Sphalerite (fig. H7B) is an important source of gallium to be high in carbonate-hosted replacement deposits and
in spite of the generally low concentrations in natural samples Mississippi Valley-type deposits, and variably enriched in
(table H3) because it is abundant in a wide variety of mineral clastic-dominated systems and volcanogenic massive sulfide
deposits (table H4). Gallium enrichment in sphalerite under deposits, whereas skarns are universally low in gallium (Cook
hydrothermal conditions results from its weak chalcophile and others, 2009). Gallium and other metals produced from
behavior, which is similar to that of zinc. Gallium is thought zinc-refining residues are derived largely from such deposits
to be incorporated in sphalerite by a coupled substitution of as the Red Dog zinc mine in Alaska (Tervek and Fay, 1986).
two Zn for Ga plus either Ag, Cu, Ge, In, or Sn to maintain Other sources include volcanogenic massive sulfide deposits;
a balanced charge (Johan and others, 1983; Johan, 1988; for example, the Tizapa Mine in Mexico (Dowa Holdings
Cook and others, 2009). The highest known concentrations Co., Ltd., 2013). Carbonate-hosted lead-zinc deposits of the
of gallium in sphalerite (2.1 to 3.7 weight percent gallium Kipushi-type—for example, the Apex Mine in Utah—have
occur in sulfide nodules in the Qingzhen (EH3) chondrite the potential to produce gallium (and germanium) as a
(Rambaldi and others, 1986), which is a range that matches primary product. The two major types of gallium sources—
experimental determinations (Krämer and others, 1987; bauxite deposits and sediment-hosted lead-zinc deposits—
Ueno and Scott, 2002). Sphalerite from gallium-rich low are described below.
temperature carbonate-hosted lead-zinc deposits of Namibia
(Khusib Spring Mine in the Otjozondjupa Region and the
Tsumeb Mine) show a range of from hundreds to more than Bauxite Deposits
3,000 ppm gallium (Melcher and others, 2006). In general, Bauxite is mined for a number of products that have
however, concentrations in most sphalerites rarely exceed commercial application in abrasive, cement, chemical,
100 ppm gallium. For example, sphalerite from clastic- metallurgical, and refractory industries. Approximately
dominated lead-zinc deposits of the Red Dog Mine in the 70 to 80 percent of the world’s dry bauxite production is
Northwest Arctic Borough of Alaska contains an average processed into aluminum metal (Freyssinet and others, 2005),
of 26 ppm gallium (Alaska Department of Environmental and these are the ores from which most gallium metal is
Conservation, 2005), whereas zinc ores from U.S. Mississippi currently derived. Bauxite is a rock that consists mostly of
Valley-type deposits average about 50 ppm gallium (Moskalyk, fine-grained aluminum minerals, notably boehmite, diaspore,
2003). Gallium contents can vary widely in volcanogenic and gibbsite, in mixtures with lesser amounts of iron oxides,
massive sulfide deposits, even within a single district or within typically goethite and hematite, kaolinite, and small amounts
individual sphalerite grains from a deposit. For example, some of anatase (Bárdossy and Aleva, 1990). Some bauxites form as
individual deposits within the Bonnifield mining district in accumulations of clayey remnants within paleokarst discon-
Alaska (such as the Anderson Mountain deposit in Denali formities in limestone sequences; these are referred to as karst
Borough and the Fosters Creek zone) can contain anywhere bauxites (fig. H5A). Karst bauxite is typically black to gray in
from 20 to 275 ppm gallium in sphalerite, whereas others (the color because of the presence of admixed organic matter and,
West Tundra Flats deposit in Southeast Fairbanks Borough) in some instances, minerals that form in chemically reduced
have less than 1 ppm gallium in sphalerite (Foley and others, environments, such as pyrite (Bárdossy, 1982). Another type
2008; Dusel-Bacon and others, 2011; Dusel-Bacon and of bauxite, lateritic bauxite, occurs in parts of thick altered
others, 2012). Sphalerite from the Callahan Mine in Hancock profiles formed by lateritization of aluminosilicate rocks
County, Maine (Ayuso and others, 2013), shows a range of (fig. H5B) (Retallack, 2010). Lateritization is a complex
from less than 3 ppm to up to 105 ppm gallium in single, integration of surficial biological, chemical, and physical
1- to 5-millimeter (mm)-wide crystals (table H3). processes that result in thick sequences of intensely weathered
saprolite and soil. Laterites are a form of ferricrete that can
Deposit Types occur as horizons within a soil profile. By definition, periods
of lateritization record exceptionally intense, regionally
The principal deposit types (table H4) and significant widespread weathering under tropical temperature regimes
global and domestic deposits (fig. H4) from which gallium with ample water (Bárdossy and Aleva, 1990); thus, lateritic
metal is currently being obtained are emphasized here; however, bauxites occur in thick profiles formed by deep tropical
other deposit types that have gallium in potentially extractable weathering. A combination of climate, tectonics, geomor-
amounts are included in table H4. Although gallium is found phology, and hydrogeological factors are required to produce
in a diverse group of mineral deposit types, current sources deposits that make up productive bauxite ore districts and
are limited to a small number of deposit types because gallium provinces (fig. H4; Bogatyrev, Zhukov, and Tsekhovsky, 2009).
Table H4. Significant global and domestic deposit types from which gallium is obtained or is potentially extractable.— Continued
[VMS, volcanogenic massive sulfide; Elements: Au, gold; Ag, silver; Al, aluminum; As, arsenic; Cd, cadmium; Co, cobalt; Cu, copper; Ga, gallium; Ge, germanium; Hg, mercury; In, indium; Pb, lead; Zn, zinc]
Principal Description
Petrologic association commodity Tectonic/deposit character Primary references
(byproduct) Example deposits/occurrences Gallium host mineralogy
Hydrothermal, Au Active epithermal gold-depositing Taupo Volcanic Zone, Rotokawa geothermal Muds and sinters of Crump (1994)
hot springs environments system, New Zealand geothermal fields;
alunite, other aluminous
phosphate minerals
High-sulfidation Au Aluminum-phophate-sulfate minerals Hugo Dummett porphyry copper-gold deposit, Aluminosilicate minerals, Khashgerel and others
epithermal occurring in the advanced argillic Mongolia; Agios Philippos Mine, Kirki, alunite, other aluminous (2008); Melfos and
gold zone of alteration Greece; Lavrion intrusion-related deposit, phosphate minerals, Voudouris (2012)
Plaka deposit, Greece aluminum hydroxide
Epithermal Au, Ag, Hg Tertiary age andesite and rhyolite Gold Canyon’s Cordero Gallium Project, Alunite, other aluminous Rytuba and others
mercury volcanic flows McDermitt, Nevada, United States phosphate minerals (2003)
Volcanogenic Zn, Cu, Pb Submarine volcanoes of backarc basins Tizapa zinc mine, Mexico; Bonnifield Sphalerite Shanks and Thurston
Volcanic-hosted, hydrothermal
massive (Au, Ag) district, Alaska; Bald Mountain, (2012); Dusel-
sulfide Maine, United States Bacon and others

(2012)
Clastic- Zn, Pb, Cu, Clastic-dominated lead-zinc ores, which are Red Dog zinc mine, Howards Pass, Su-Lik, Sphalerite Leach, Bradley, and
dominated Ag (Ga, In, hosted in shale, sandstone, siltstone, or and Anarraaq, Alaska, United States; others (2010);
lead-zinc Ge) mixed clastic rocks, or occur as carbonate Sullivan, British Columbia, Canada; Leach, Taylor,
replacement, within a clastic-dominated Broken Hill, Australia; Balmat-Edwards, and others (2010);
sedimentary rock sequence New York, United States; Rammelsberg, Taylor and others
Meggen, Germany (2009)
Mississippi Pb, Zn, Cu, Carbonate-hosted lead-zinc deposits, Tri-State area in the United States (Southeast- Sphalerite Leach, Bradley, and
Valley-type (Ge, Ag, Ga, which are typically found in platform ern Missouri, Eastern and Central Tennessee, others (2010);
As, Cd) carbonate sequences in passive-margin Northern Arkansas); Pine Point, Canada; Leach, Taylor,
tectonic settings Polaris, Nanisivik, Alaska, United States; and others (2010);
Navan, Ireland Taylor and others
(2009)
Sediment-hosted
Carbonate- Cu, Pb, Zn Carbonate-hosted (karstic) polymetallic Grinnell and Kanuyak Island, Northwest Sphalerite Söhnge (1964);
hosted (Co, Ge, Ag, deposits found in intracratonic platform Territories, Canada; Gortdrum, Ireland; Intiomale and
Cu±Pb±Zn Ga, As, Cd) and rifted continental margin sedimentary M’Passa, Republic of the Congo; Timna, Oosterbosch
(alt. Tsumeb sequences; typically folded and locally Israel; Nifty, Australia; portions of the (1974); Bernstein
or Kipushi) faulted; often overlain disconformably by Dongchuan deposits, China; Ruby Creek (1986)
oxidized sandstone-siltstone-shale units. and Omar deposits, Alaska, United States;
Largest deposits are epigenitic replace- Tsumeb and Kombat, Namibia; Kipushi,
ments within thick sedimentary sequences Democratic Republic of the Congo;
Apex Mine, Utah, United States
Table H4. Significant global and domestic deposit types from which gallium is obtained or is potentially extractable.— Continued
[VMS, volcanogenic massive sulfide; Elements: Au, gold; Ag, silver; Al, aluminum; As, arsenic; Cd, cadmium; Co, cobalt; Cu, copper; Ga, gallium; Ge, germanium; Hg, mercury; In, indium; Pb, lead; Zn, zinc]
Principal Description
Petrologic association commodity Tectonic/deposit character Primary references
(byproduct) Example deposits/occurrences Gallium host mineralogy
Bauxite, karstic Al (Ga) Formed by deep, in situ weathering, transport, Europe (France, Croatia, Italy); Jamaica; Gibbsite, diaspore, Freyssinet and others
and accumulation of intercalated clays or bauxite mine in Arkansas, United States; boehmite (2005); Retallack
by clay dissolution residues of limestone China (2010); Bárdossy
or other carbonate rocks, karst setting, accu- (1982), Bogatyrev,
mulation of aluminum hydroxide minerals Zhukov, and Tsek-
hovsky (2009)
Bauxite, lateritic Al (Ga) Formed by lateritization of various predomi- Major bauxite provinces; mostly in the Gibbsite, diaspore, Freyssinet and others
nately silicate rocks such as granite, gneiss, countries of the tropics (current and paleo): boehmite (2005); Retallack
basalt, syenite, and shale. Intense mineral (1) the South American province. includes (2010); Bárdossy
hydrolysis resulting in kaolinite dissolution the Guiana shield (Guyana, French Guiana, and Aleva (1990);
and precipitation of aluminum hydroxide Suriname) and the central Brazilian shield; Bogatyrev, Zhukov,
minerals (2) the West African province, includes Guinea, and Tsekhovsky
Ivory Coast, Burkina Faso, Sierra Leone, (2009)
Ghana, and Mali; (3) the Indian province,
includes both the western and eastern coasts
of India; (4) the South East Asian province,
includes Vietnam, Laos, and Cambodia; and
(5) the Austalian province. Minor provinces
Weathering-related
include the southern United States and the south-
ern Ural Mountains (Russia and Kazakhstan)
Supergene, Ge, Ga Gossans and other oxidized zones of copper- Apex Mine, Utah, United States; see Jarosite, Fe-hydroxide, Bernstein (1986);
gossan rich, arsenic-bearing sulfide deposits, Carbonate-hosted Cu ± Pb ± Zn, Ga-hydroxides Dutrizac and others
particularly those of the carbonate hosted Kipushi-type (1986)
polymetallic Kipushi-type rocks
Coal Coal (Ga?) Coal seams and waste products from coal- Jungar Coalfield, Inner Mongolia; Coal, fly ash, kaolinite, Finkelman (1993)
fired powerplants; gallium is enriched West Virginia, United States; Canada boehmite
in fly ash, sometimes 6 to 10 times
more than in the feed coal
Geology H17
The formation of large and superlarge deposits is thought to (soils, kaolins, and ball clays) derived from deep weathering
require more than 10 million years or the superposition of of crustal rocks. Overall, bauxite contains concentrations in
several intense weathering epochs. the range of 8 to 800 ppm gallium, with most values in the
Various models for the origin of laterites and lateritic range 40 to 80 ppm gallium (table H2). The world average
bauxites (for example, McFarlane, 1976; Brimhall and others, concentration of gallium in bauxite was initially estimated
1991; Retallack, 2010) have included both (a) elemental to be 52 ppm (Burton and Culkin, 1978), and additional
removal by hydrolysis and chemical leaching, and data have not changed that value significantly. For example,
(b) elemental addition by mineral precipitation or fluvial or carbonate-hosted bauxites from central and southern
atmospheric deposition (for example, eolian dust) to explain Europe display average concentrations of about 50 ppm
the chemical compositions and volume and mass losses gallium (Schroll, 1999); bauxites from Arkansas range from
in bauxites. Bauxites usually form in the pallid soil zone 50 to 100 ppm gallium (average 86 ppm); and bauxite from
(fig. H5B) but can occur in the B or C horizons of exceptionally India has a similar range of 5 to 122 ppm gallium (table H2).
thick profiles (Retallack, 2010). Lateritic bauxites typically have High gallium values are reported in bauxite originating from
distinctive pisolitic textures and red colors (fig. H7A). Karst alteration of alkali rocks (for example, nepheline syenite of
bauxites that form by transport and redeposition of lateritic Russia ranges up to 170 ppm gallium) and in some unusual
bauxite clays and rubble in paleokarst depressions may retain karst deposits (table H2). In general, however, there appear
the laterite characteristics of color and texture (Retallack, to be no significant differences in gallium concentrations of
2010). The extreme weathering conditions that contribute to karst- or lateritic-type bauxites (Schulte and Foley, 2014).
bauxite formation remove virtually all the alkalis and alkaline
earths, leaving only the relatively immobile component of the Sediment-Hosted Lead-Zinc Deposits
original rock; as a result, paleosols within bauxites and soils
that form on bauxite are classified as oxisols (U.S. Natural Sediment-hosted lead-zinc deposits are historically
Resources Conservation Service, Soil Survey Staff, 2000). the most significant sources of zinc, and these deposits are
Bauxite deposits form in a diverse array of geologic and mined throughout the United States and the world (Leach,
tectonic environments over a wide range of geologic time Bradley, and others, 2010). The largest and most economically
(for example, Bárdossy, 1982; Bárdossy and Aleva, 1990; important sediment-hosted deposits for zinc production are
Retallack, 2010). An extensive study of well-characterized the clastic-rock-dominated and carbonate-rock-dominated
and dated bauxites (Retallack, 2010) showed that although the (Mississippi Valley-type) subtypes (Leach, Marsh, and others,
oldest known bauxites formed on the Arabian Shield at about 2004; Leach, Bradley, and others, 2010; Leach, Taylor, and
3,500 mega-annum (Ma, or million years ago), bauxites are others, 2010); these are the main types of sulfide deposits
most abundant in rocks formed since about 100 Ma owing to from which gallium metal is obtained at present because they
better preservation of the rock record (Wilkinson and others, are currently the predominant sources of zinc ore. Carbonate-
2009). Bauxites show an uneven distribution through time that hosted polymetallic deposits of the Kipushi (or Tsumeb) type
is consistent with evidence supporting their correlation with are of minor importance for zinc production; however, they
paleoclimatic events of intense weathering, possibly related are considered separately here because they have high gallium
to greenhouse gas emissions, which lasted for geologic time content relative to other deposit types of the sediment-hosted
intervals of less than about 100,000 years (Valeton, 1983; class and are historic gallium producers for the United States.
Retallack, 2010). Bauxite formation during these events Much of the following discussion is summarized from a
had an expanded distribution from the Quaternary (between number of seminal review studies of sediment-hosted lead-
the Tropics of Cancer and Capricorn) to encompass areas zinc deposits, including Leach and Sangster (1993), Leach,
near the Arctic and Antarctic Circles (Retallack, 2010). As a Viets, and others (1995); Leach, Marsh, and others (2005);
consequence, greenhouse gas events of the past, which are Leach, Sangster, and others, (2005); Groves and Bierlein
shown to have influenced the distribution of aluminum ores (2007); Leach, Bradley, and others (2010); and Leach, Taylor,
(Retallack, 2010), are also associated with gallium ores. and others (2010).
Bauxite, lateritic bauxite, and karst bauxite are rocks that Sediment-hosted lead-zinc deposits form in rocks
have concentrations of aluminum exceeding about 45 percent of widely varying geologic age and tectonic environment
by weight, by definition (Valeton, 1972). This reflects a high (figs. H5C through H5E). In general, these deposits are hosted
proportion of hydroxide minerals with aluminum contents by large-scale sedimentary systems consisting of a variety of
on the order of about 60 or more percent alumina by weight. siliciclastic and carbonate rocks and have no direct genetic
Bauxite generally is defined as rock with 20 percent or less association with igneous activity. Many deposits in the
total iron, whereas lateritic bauxite, in addition to a high sediment-hosted class display transitional features, and the
percentage of aluminum, can have greater than 20 percent distinctions among some of the deposit types are subjective.
total iron, which is generally ferric owing to oxidation unless Most sediment-hosted deposits occur in sedimentary rock
reducing conditions prevail locally. The limited mobility of sequences that were originally deposited in extensional rift
aluminum and gallium in near-surface environments accounts or passive-margin settings. There is an apparent uneven
for gallium enrichment in bauxite and related materials distribution of sediment-hosted deposits through time that is
Geology H19
attributed to their genesis in large-scale sedimentary systems deposited sphalerite at the Red Dog deposit in Alaska had
and to continued recycling of the sedimentary rock record temperatures in the range of 100 to 200 °C and salinities
within the evolving tectonic and geochemical systems of Earth from 14 to 19 weight percent NaCl equivalent (Leach, Marsh,
through geologic time. Tectonic setting, depositional environ- and others, 2004). The dominant sulfide minerals present
ment, and host-rock lithology influence the mineral chemistry are sphalerite (which is generally the most common sulfide
of the contained sulfide minerals, including their trace element mineral) and lesser amounts of galena and the iron sulfides,
characteristics. The ores consist mainly of galena, sphalerite, marcasite, pyrite, or pyrrhotite; chalcopyrite and sulfosalt
and generally lesser amounts of iron sulfides, which may minerals may be present in minor amounts (Large, 1981, 1983;
be marcasite or pyrite. In addition to lead and zinc, gallium, Lydon, 1983; Large and others, 2005). The sulfide minerals
germanium, and silver can be important constituents; copper form lens-like bodies that are interbedded with fine-grained
is generally quite low, except in the Kipushi-type deposits, dark clastic and chemical sedimentary rocks. Carbonate
but can be economically important in all these deposits. minerals (ankerite, calcite, dolomite, and siderite), barite and
Laminated ore textures and a layered morphology are quartz, siliceous shale, and low-grade silica-replaced rocks
generally characteristic of clastic-dominated deposits, whereas are common and can be gradational into massive ore. Ore
Mississippi Valley-type deposits generally exhibit abundant from these deposits (table H4) generally contains less than
evidence for epigenetic and replacement ores. Nonetheless, 100 ppm gallium, with a typical range of 5 to 50 ppm gallium
some clastic-dominated ores show replaced sediments in (table H2). For example, the Red Dog deposit (fig. H4) is
early or burial diagenetic environments and some Mississippi hosted by organic-rich mudstone and shale of the Mississippian
Valley-type deposits display laminated ore textures. Kuna Formation (Kelley and others, 2004), and zinc concen-
trate from the deposit has 26 ppm gallium (Alaska Department
Clastic-Dominated Lead-Zinc Type of Environmental Conservation, 2005). Other elements in
association with clastic-dominated lead-zinc deposits include
The most definitive characteristic of clastic-dominated Ag, Al, As, Au, B, Ba, Cd, Co, Cu, Fe, Ge, Hg, Mn, Mo, Ni,
deposits as described by Leach, Marsh, and others (2005) and Sb (Briskey, 1986; Kelley and others, 1995).
is their occurrence in clastic rock-dominated sedimentary
sequences formed mainly in passive margins, continental
Mississippi Valley Lead-Zinc Type
rifts, continental sag basins, and back-arc basins (figs. H5C
and H5D). The orebodies are typically hosted in (in order Carbonate-hosted lead-zinc deposits are found throughout
of predominance) shale, sandstone, siltstone, carbonate, or the world, and large famous examples occur in central North
mixed clastic rocks and their metamorphosed equivalents. America; hence, they are generally referred to as Mississippi
They may also occur as carbonate replacement ores within Valley-type deposits. The most important characteristics of
a clastic-rock-dominated sedimentary sequence. Mississippi Valley-type deposits (Sangster, 1990; Leach and
The vast majority of clastic-dominated deposits Sangster, 1993; Leach, Sangster, and others, 2005) are that
globally occur in Proterozoic basins that formed between they occur globally in dolostone and limestone that formed in
2.02 billion years ago—the age of the earliest known deposit platform carbonate sequences. They are commonly related to
of these ores—and about 1.85 to 1.58 billion years ago, extensional domains inboard of contractional tectonic belts or
which reflects a major period of clastic-dominated lead-zinc continental extensional basins transitional to passive margin
deposition in Australia and India. The appearance of clastic- basins (figs. H5C and H5E). The ores are usually located
dominated deposits in the Precambrian period corresponds to at flanks of basins, orogenic forelands, or foreland thrust
a time of formation of large and long-lived basins on stable belts inboard of the clastic-rock-dominated passive margin
cratons that followed the Great Oxidation Event at about sequences. Numerous lines of evidence have established that
2.4 to 1.8 billion years ago. The formation of clastic-dominated the metals were carried in fluids derived mainly from evapo-
deposits is related to enhanced oxidation of sulfides in the crust rated seawater and driven within the carbonate sequences by
(which released sulfate to the hydrosphere and lead and zinc to large-scale tectonic events.
sediments); the development of major redox and compositional More than 80 percent of Mississippi Valley-type deposits
gradients in the oceans; the first formation of significant sulfate- are hosted by rocks formed during the Phanerozoic Eon;
bearing evaporates, red beds, and oxidized aquifers; and the less than 20 percent occur in Precambrian rocks (Sangster,
evolution of sulfate-reducing bacteria (Leach, Bradley, and 1990; Leach, Bradley, and others, 2001; Leach, Sangster, and
others, 2010, p. 593). A number of clastic-dominated lead-zinc others, 2005; Kesler and Reich, 2006). Increased oxygenation
deposits also formed during the Carboniferous Period along of the oceans following the second oxidation event of the
passive margins in sedimentary-evaporite belts of Pangea and atmosphere in the late Neoproterozoic Era led to an abundance
were deposited after the second oxidation event. of evaporites, oxidized brines, and a dramatic increase in
Mineralogical and geochemical evidence suggests that the volume of coarse-grained and permeable carbonates in
clastic-dominated ore fluids were principally hot metalli Paleozoic carbonate platforms. Most Phanerozoic-hosted
ferous basinal brines (for example, Badham, 1981; Lydon, Mississippi Valley-type deposits formed in the carbonate
1983; Cooke and others, 2000). For example, the brines that platform sequences during Devonian to Permian time as a
result of tectonic events generated by the assimilation of Features of Kipushi-type deposits that are similar to
Pangea. A lesser number formed during Cretaceous to Tertiary aspects of clastic-dominated-type and Mississippi Valley-type
time when microplate assimilation affected the western margin deposits include the general platform carbonate setting, a lack
of North America and Africa-Eurasia. of spatially associated igneous intrusions, regional-scale ore
These ores consist mainly of galena, sphalerite, and fluid migration (as evidenced by the widespread occurrence
generally lesser amounts of iron sulfides. Copper and silver are of mineralization over thousands of square kilometers in the
important constituents in some of these deposits (for example, largest deposits), and ore localization in solution collapse
deposits of the Irish subtype and some deposits of the breccias. The orebody at Kipushi-type deposits forms a
Viburnum Trend). Gangue minerals are dominantly carbonates highly irregular subvertical pipe at the faulted boundary
(ankerite, calcite, dolomite, and siderite), with typically minor of dolomitic shale and marine dolomite, commonly within
amounts of barite. Silicification of the host rocks (or quartz breccia zones, and prospecting for copper-rich ores is
gangue) is generally minor, but may be abundant in a few focused on paleokarst structures that are possibly related to
deposits. Minor minerals associated with Mississippi Valley- salt diapirs (Intiomale and Oosterbosch, 1974). The Khusib
type mineralization differ widely between individual districts, Springs deposit, which is a lens-shaped sulfide orebody up to
and minor and trace metals also vary (Lavery and others, 10 meters in thickness and elongated parallel to the bedding,
1994). Minor elements and element associations can include replaces locally brecciated limestone of the lower Tsumeb
Ag, As, Au, Ba, Bi, Cd, Co, Cu, Ga, Ge, In, Fe, Hg, Mn, Mo, subgroup. The origin of the breccia pipes is probably related
Ni, Sb, Sn, and Tl (Hall and Heyl, 1968; Hagni, 1983; Viets to the erosion and karstification of the Hüttenberg Formation
and others, 1992; Leach, Taylor, and others, 2010). (Hughes and others, 1984; Hughes, 1987); however, there is
In Mississippi Valley-type deposits, gallium is primarily some evidence that hydrothermal brecciation and silicification
in sphalerite, which typically can contain from 0.02 to more occurred during mineralization (Chetty and Frimmel, 2000;
than 500 ppm gallium (table H4). The overall content of Kamona and Günzel, 2007). Fluid inclusion studies have also
gallium in studied deposits averages about 58 ppm; however, established that mineralizing fluids for Kipushi-type deposits
averages for individual deposits can vary widely, from are comparable to or higher than those of typical Mississippi
6 to 130 ppm gallium. Valley-type deposits and clastic-dominated lead-zinc deposits
(see above). Ore-stage minerals contain highly saline fluids
(17 to 43 weight percent NaCl equivalent) in inclusions
Kipushi Polymetallic Type
with homogenization temperatures that vary from about
Kipushi-type deposits are relatively rare, epigenetic, 100 to 380 °C; the fluids were generated in postorogenic,
discordant deposits of Cu–Zn–Pb –Ag–As–Sb–Ge–Ga-bearing extensional settings (Misiewicz, 1988; Chetty and Frimmel,
ores that occur in carbonate platform rock sequences and are 2000; Selby and others, 2009; Haest and others, 2009;
typically associated with karst, solution collapse breccias, van Wilderode and others, 2012).
and related features, such as salt diapirs (fig. H5F; Hitzman Kipushi-type deposits are distinguished from Mississippi
and others, 2005). The most important characteristics of these Valley-type deposits by having significantly higher trace
deposits are their geologic setting and distinctive polymetallic element concentrations and more diverse mineralogy
mineralogy. Considerable controversy remains concerning (Frimmel and others, 1996). Primary minerals include
whether these deposits have an igneous affinity; however, enargite, galena, and pyrite, and a zinc-rich tennantite;
most are classified as sediment-hosted deposits. Deposits of locally abundant zones of bornite, chalcocite-digenite, and
the Kipushi type (fig. H4) include world-class polymetallic chalcopyrite; galena, pyrite (cobaltiferous), pyrrhotite, and
orebodies at Tsumeb and Khusib Springs in Namibia (Söhnge, iron-poor sphalerite. Late-stage phases include carrollite
1964), and at Kipushi (in the Democratic Republic of the and copper-thiogermanate minerals, pearceite-polybasite,
Congo) in the Zaire-Zambia copper belt (Intiomale and native silver, tetrahedrite, and silver-tennantite. Additional
Oosterbosch, 1974). Domestic deposits of this type include minerals identified in some deposits include covellite, a
orebodies at the Ruby Creek Mine in Alaska (Hitzman, 1986; tungsten-bearing germanite, germanium-bearing stannoidite,
Bernstein and Cox, 1986; Selby and others, 2009) and at the and stromeyerite. Gangue minerals include barite and barium-
Apex Mine in Utah (Bernstein, 1986). Other large deposits silicate minerals, calcite, chlorite, dolomite, fluorite, sparse
included in this group in the past are, in Australia, the Mount quartz, and siderite. Ore minerals in Kipushi-type deposits
Isa Mine in the State of Queensland, and the Cooley and Ridge can have gallium contents that range from hundreds of parts
deposits of the McArthur River Mine in the Northern Territory per million gallium to about 60 weight percent gallium
(Bernstein and Cox, 1986; Hitzman, 1986; Selby and others, (tables H2 and H3). Compared with other sediment-hosted
2009); more recent studies, however, suggest that these deposits ore systems, Kipushi-type deposits are characterized by
are better classified as clastic-dominated-type deposits because marked enrichments in germanium and rhenium (Schneider
they are mainly lead-zinc orebodies in dolomitic siltstones, and others, 2007). Many weathered deposits of this type
mudstones, and sandstones formed in a continental sag basin contain gallium-bearing secondary minerals formed largely
(Cooke and others, 2000; Leach, Marsh, and others, 2005; through supergene processes (table H3). For example, at the
Leach, Bradley, and others, 2010; Taylor and others, 2009). Apex Mine in Utah, the primary ore is inferred to be similar
Resources and Production H21
to bornite-chalcopyrite-tennantite-galena-sphalerite ore of gallium in source materials. Factors controlling gallium

a Kipushi type, although the Apex orebodies are almost recovery are typically proprietary, and scant literature is avail-
completely oxidized to germanium-bearing hydrogoethite and able on the general operating practices of companies involved
gallium-bearing (up to about 1 percent gallium) jarosite. in gallium production. The potential remains for additional
gallium production given more efficient and improved extrac-
tion technologies and market-driven economic incentives.
Resources and Production
Undiscovered Resources
Identified Resources
The USGS has conducted no quantitative mineral
The U.S. Geological Survey (USGS) estimates that world resource assessments focused on undiscovered domestic or
resources of gallium in bauxite exceed 1 billion kilograms global resources of bauxite since the work of Patterson and
and that a considerable quantity of gallium could be present others (1986). Because the major bauxite provinces of the
in world zinc resources (Bray, 2013). Using USGS information world are well established and have been intensely explored,
coupled with data on global bauxite provinces (Bogatyrev most of the significant bauxite deposits globally are thought
and Zhukov, 2009), comparable estimates of geologically to be known (Freyssinet and others, 2005). The major
available gallium in bauxite reserves and resources (of nearly bauxite provinces (fig. H4) occur in the following five major
1.4 million metric tons and 4 million metric tons, respectively) regions: (a) the South American region—the Guiana shield
have been suggested (Dittrich and others, 2011). Analogous (French Guiana, Guyana, Suriname) and the central Brazilian
estimates of world resources of gallium in zinc resources have shield; (b) the West African region—Burkina Faso, Ghana,
not been made owing to insufficient data. The United States Guinea, Ivory Coast, Mali, and Sierra Leone; (c) the Indian
is expected to meet its current and expected future needs region—the western and eastern coasts; (d) Southeast Asia—
for gallium through imports of primary gallium from these Cambodia, Laos, and Vietnam; and (e) the Australian region.
resources, from imports of recycled and refined gallium, and Other bauxite provinces occur in the southern United States
from domestic production of recycled and refined gallium. (Arkansas region), the Caribbean, the southern Ural Mountains
Identified bauxite resources of the world are about (Russia and Kazakhstan), and China.
55 to 75 billion metric tons and occur in Africa (32 percent), The most recent USGS National Mineral Resource
Oceania (23 percent), South America and the Caribbean Assessment identified areas of the United States that have
(21 percent), Asia (18 percent), and elsewhere (6 percent) significant potential for undiscovered resources of zinc
(Bray, 2012). Lateritic bauxite deposits make up approximately (Schruben, 2002). The estimate of the amount of zinc
90 percent of global bauxite resources, and aluminum produc- in undiscovered U.S. deposits ranged from a 90-percent
tion is mainly from these deposits (Freyssinet and others, probability of at least 130 million metric tons to a 10-percent
2005). Karst bauxite deposits are more scattered in distribution probability of at least 290 million metric tons. The mean esti-
and are mined mainly in eastern Europe and the Caribbean mate of zinc in undiscovered deposits was 210 million metric
islands (Bárdossy, 1982). Domestic bauxite deposits consist tons. Nearly 40 percent of the zinc was thought to be contained
mainly of subeconomic resources that are not generally suit- in undiscovered Mississippi Valley-type deposits. Other
able for alumina production owing to their high silica content; major deposit types were sedimentary exhalative (31 percent),
thus, recovery of gallium from these deposits is unlikely. volcanogenic massive sulfide (15 percent), and polymetallic
Although domestic resources of bauxite are inadequate to meet replacement (8 percent) deposit types. At that time, the total
either short- or long-term U.S. demand, the United States has identified zinc resources in the United States were estimated
essentially inexhaustible subeconomic resources of aluminum to be 99 million metric tons. No comparable estimates of
in materials other than bauxite. These are primarily clay undiscovered global resources of zinc have been made.
deposits, which also contain gallium in amounts comparable to
those of bauxite (30 to 50 ppm gallium) (table H2). Identified
zinc resources of the world are about 1.9 billion metric tons Production
(Tolcin, 2013). Mississippi Valley-type deposits, which are
widespread in North America, account for about 38 percent In 2012, world primary gallium production was
of the global resources of lead and zinc in sediment-hosted estimated to be 273 metric tons (fig. H4A). China, Germany,
ore deposits; significant zinc resources are also contained in Kazakhstan, and Ukraine were the leading producers; coun-
clastic-dominated deposits of Alaska (fig. H4; Leach, Marsh, tries with lesser output were Hungary, Japan, the Republic of
and others, 2005). Korea, and Russia. Refined gallium production was estimated
The estimates given here apply to total gallium content; to be about 354 metric tons; this estimate includes primary
only a small percentage of gallium metal in bauxite and zinc gallium production and some scrap refining. China, Japan,
ores is recoverable using current methods because processing the United Kingdom, and the United States were the principal
techniques to separate aluminum, zinc, and other byproduct producers of refined gallium. Gallium was recycled from new
metals (for example, germanium and indium) compete for scrap in Canada, Germany, Japan, the United Kingdom, and
the United States. World primary gallium production capacity more than 90 million metric tons of 1.2 percent copper, plus
in 2012 was estimated to be 474 metric tons; refinery capacity, elevated contents of silver, cobalt, germanium, gallium, and
270 metric tons; and recycling capacity, 198 metric tons zinc (Hitzman, 1986). The metacarbonate sequence consists
(Jaskula, 2013a). Imports of gallium into Japan and the primarily of thin-bedded to massive metadolostone and
United States (the two leading consuming countries) were marble that is locally graphitic or phyllitic and contains thin
used as the basis for estimating world gallium production. micaceous layers interpreted as airfall tuffs (Hitzman, 1986;
In addition, Metal Bulletin (2013) provided an updated Hitzman and others, 1986). The presence of coeval volcano-
Chinese gallium production estimate, expanding the estimate genic massive sulfide deposits just north of the Ruby Creek
of China’s production considerably owing to the substantial deposit is possible evidence for regionally extensive hydro-
capacity increases of China’s gallium operations (fig. H4B). thermal activity, perhaps related to igneous activity associated
No domestic production of primary gallium was with continental extension (Hitzman and others, 1986; Selby
reported in 2012. Molycorp Inc. recovered gallium from and others, 2009).
scrap materials, predominantly those generated during the
Apex deposit, southwestern Utah.—This deposit has served
production of GaAs. Molycorp’s facility in Blanding, Utah,
as the only primary source in the world for the production of
has the capability to produce about 50 metric tons per year of
gallium and germanium. The Apex Mine operated intermittently
high-purity gallium. The company recovered gallium from
from 1884 to 1962, and more than 7,000 metric tons of copper,
its customers’ scrap on a fee basis and purchased scrap and
5,600 kilograms of silver, and small amounts of gold and lead
low-purity gallium for processing into high-purity material.
were produced. The mine was reopened in 1985 with plans to
produce gallium and germanium (Washington County Historical
Society, 2013). At that time, the mine was estimated to contain
Exploration for New Deposits 220,000 metric tons of ore grading 0.064 percent germanium,
0.032 percent gallium, 1.63 percent copper, 0.77 percent
Most domestic exploration for gallium is done as
lead, 1.58 percent zinc, 0.50 percent arsenic, 16.73 percent
a second-order effort related to new discoveries of zinc
iron, and 38 grams per metric ton silver (Bernstein, 1986).
resources because U.S. bauxite resources are currently
Surface dumps from the old mine contained an additional
subeconomic. Exploration is active in the United States and
45,000 metric tons of material grading 0.037 percent
globally for all types of large-tonnage zinc deposits, which
germanium, 0.019 percent gallium, and 1.55 percent copper.
constitute a major source for gallium (Emsbo, 2009; Taylor
Similar deposits may occur in association with copper
and others, 2009; Leach, Bradley, and others, 2010). There is
in fault-hosted breccias in Pennsylvanian limestone near
some evidence that partitioning of gallium may be influenced
Hansonburg, New Mexico (Eveleth and Lueth, 2009).
by the amount of sphalerite in bulk ore, leading to a dilution
effect, such that the largest zinc deposits of a given type Cordero Gallium Project, Humboldt County, Nevada.—This
may be expected to have relatively lower gallium contents project is reportedly North America’s largest known primary
(Cook and others, 2009). This, however, may have little effect gallium occurrence (Rêserva International LLC, 2008).
on resource estimation because economic factors that support Anomalous gallium mineralization occurs over a wide area
gallium extraction are tilted in favor of large tonnage values in and around the historic Cordero and McDermitt mercury
for the principal commodity over small changes in grade for mines. There are indications that a number of high-grade
a byproduct element. The most gallium-enriched sediment- “feeder zones” occur through the deposit, which also hosts
hosted ores are the Kipushi-type deposits, which are mined significant occurrences of rare-earth elements. The resources
for copper, lead, silver, and zinc and byproduct antimony, for the project above a cutoff grade of 30 ppm gallium are esti-
arsenic, germanium, and gallium; some deposits of this group mated to exceed 13 million metric tons (Rêserva International
may contain gallium (and germanium) in amounts that justify LLC, 2008).
extraction as a primary product. Active exploration efforts are
underway in the major Kipushi-type provinces of the Central
African copperbelt—Kipushi and Tsumeb. Important domestic
examples of Kipushi-type deposits include the Ruby Creek Environmental Considerations
deposit in Alaska and the Apex deposit in Utah. Additional
domestic exploration efforts are focused on gallium resources Sources and Fate in the Environment
associated with epithermal mineralized and hydrothermally In weathering environments, gallium is generally
altered volcanic rock suites. immobile and is only slightly less reactive than aluminum
Ruby Creek deposit, Alaska.—This deposit is located along the (Shiller and Frilot, 1996). The tendency for gallium to be
northern flank of the Cosmos Hills near the boundary between dissolved and transported depends upon its chemical form,
a carbonate platform and a shale basin within the Ambler which in turn depends largely upon the pH and temperature
district. The 1-kilometer-diameter body of hydrothermal of weathering solutions. Gallium associated with bauxite at
dolostone is one of several similarly mineralized occur- a pH near 4 and a weathering solution temperature of 25 ºC
rences in the Cosmos Hills. The Ruby Creek deposit contains would be expected to remain as a solid (for example, Ga(OH)3
Environmental Considerations H23
or GaO(OH)), but can theoretically dissolve to form aqueous industrial areas (Chen, 2007; Kabata-Pendias and Mukherjee,
hydroxide complexes (Ga(OH)3 or Ga(OH)4 at pH values > 4 2007). Likewise, dissolved and colloidal concentrations of
and Ga(OH) and Ga(OH)2 at pH values < 4; Bénézeth and gallium in groundwater near semiconductor manufacturing
others, 1997; Diakonov and others, 1997). Gallium is expected areas in China have been measured to be greater than 10 µg/L
to be transported in soils, streams, and rivers in the solid phase (Chen, 2006). The recycled content, or proportion of scrap,
as small particulates because of the low solubility of gallium used in gallium production is between 10 and 25 percent, but
minerals in natural waters. the fraction of gallium in discarded products that get recycled
Gallium associated with sulfide minerals is more is less than 1 percent (Graedel and others, 2011). One of the
mobile based on the instability of sulfides at Earth’s surface. main challenges of gallium recycling is that it is commonly
Dissolution of sulfide minerals releases metals and sulfuric comingled with other “specialty metals” in high performance
acid, and the acidic pH values allow higher concentrations alloys, making recovery technologically and economically
of metals to be dissolved in solution—potentially causing unfeasible (Reck and Graedel, 2012). Given the importance of
the environmental problem known as acid mine drainage gallium in thin-film photovoltaic cells and integrated circuits,
(AMD). Under acidic conditions, gallium would most likely however, gallium recycling is likely to increase in the future
form dissolved complexes with sulfate and (or) chloride (Graedel, 2011).
(for example, GaSO4+ or GaCl−) (Wood and Samson, 2006).
Metals dissolved in AMD can be naturally attenuated through
precipitation, sorption to oxyhydroxide minerals, or dilution
Mine Waste Characteristics
by mixing with water at circumneutral pH; otherwise, metals Mine waste is generally considered to be the material
are transported downstream. that originates and accumulates at a mine site that has no
Examples of natural concentrations of gallium in soil, current economic value (Lottermoser, 2010), and it includes
water, and air are given in table H2. Gallium contents in both solid and liquid waste. Gallium associated with bauxite
soils range from 3 to 70 milligrams per kilogram (mg/kg) is usually mined by open pit or underground methods and then
(or 3 to 70 ppm) (Kabata-Pendias and Pendias, 2001), and refined through the Bayer process, which can lead to large
concentrations as high as 220 mg/kg have been observed volumes of processing waste. Based on its appearance, bauxite
in agricultural soil (Połedniok and others, 2012). Gallium (or alumina) processing waste is commonly referred to as
generally behaves like aluminum in the environment, but, red mud. Red mud depositories are connected with alumina
under certain pH and redox conditions, the two elements processing plants and are not necessarily located at the mine
may be separated. As a result, values of the ratio of gallium site. For example, four active plants in the United States
to aluminum (Ga:Al ratio) can aid in detecting gallium predominantly process alumina ore from overseas (Bray,
enrichment in various materials. Shiller and Frilot (1996) 2012). On October 4, 2010, a breached red mud depository
showed that the Ga:Al ratio of parent rocks (and residual released between 600,000 to 700,000 cubic meters of material
soils) and streambed solids were similar, whereas the Ga:Al from the Ajka Timfoldgyar Zrt alumina plant in Hungary
ratio in nearby streams was higher than those in parent (Reeves and others, 2011). This spill was unprecedented
rocks. The concentration of gallium in these streams ranged both in scale (the spill covered an estimated 800 hectares of
from 0.0001 to 0.006 micrograms per liter (µg/L) (or land [Ruyters and others, 2011]) and in its delivery of trace
0.0001 to 0.006 parts per billion). These concentrations are elements across such a vast area (Mayes and others, 2011).
generally lower than the 0.001 to 0.12 µg/L range of dissolved Bauxite ore results from extreme chemical weathering,
gallium found in large rivers around the world and are compa- and many elements that were originally present in the parent
rable to gallium concentrations measured in the Atlantic Ocean rock have been leached away. The exceptions are minor
(Shiller, 1998). Compared with dissolved species, gallium is elements that can sorb to or coprecipitate with aluminum and
highly concentrated in small particulates in river water, with iron (oxyhydr)oxide minerals that make up the ore and waste.
a global average of 18.1 mg/kg in suspended sediment (Viers For example, in addition to Al and Fe, bauxite processing
and others, 2009). Gallium occurs naturally in the atmosphere waste has been shown to contain elevated concentrations of
as part of mineral dust particles and has been measured to As, Cr, Ga, Mo, Ni, and V (Mayes and others, 2011). Bauxite
be less than 0.14 nanograms per cubic meter (ng/m3 ) at the mine and processing waste generally lacks acid-generating
South Pole (Kabata-Pendias and Pendias, 2001). minerals, so these elements are expected to remain immobile
Mining and ore processing can hasten the weathering under oxidizing and near-neutral (5 < pH < 8) weathering
process and can lead to above-background concentrations of conditions as long as abundant iron-rich particles are present
gallium in soil and water (table H2). For example, gallium (Smith and Huyck, 1999).
concentrations ranging from 93 to 270 mg/kg have been Waste products that result from mining sediment-hosted
observed in soils near bauxite and lead-zinc mine sites in deposits usually consist of waste rock, tailings piles, and
Poland (Połedniok and others, 2012). In addition, anthro possibly pit lakes. For example, the cumulative volume of
pogenic release of gallium to the atmosphere occurs during tailings generated at the Red Dog Mine, which is a clastic-
coal combustion, ore processing, and semiconductor manufac- dominated lead-zinc deposit, totaled 27.4 million metric tons
turing, leading to concentrations as high as 1 to 12 ng/m3 near in 2006, and it is projected to total 88 million metric tons
by 2031 (SRK Consulting [Canada] Inc., 2007). The largest such as cancer (Chitambar, 2010), but the long-term effects
U.S. Environmental Protection Agency Superfund site occurs of human exposure to gallium in drinking water and soil
in the Tri-State zinc mining district and contains an estimated resources remain unknown. Gallium does not appear in the
91 million metric tons of waste rock (U.S. Environmental U.S. Clean Water Act, and the Occupational Safety and Health
Protection Agency, 2006). The district contains a large number Administration (OSHA) does not consider gallium metal to be
of Mississippi Valley-type lead-zinc deposits and covers hazardous, although some State governments include gallium
approximately 1,800 square kilometers of Kansas, Oklahoma, in their right-to-know lists (Ziegler and others, 2004).
and Missouri (Leach, Taylor, and others, 2010). The Given their similar chemical characteristics, the health
mineralogy of the mine waste associated with these deposits effects of gallium may be similar to those of aluminum.
reflects the mineralogy of the unmined deposit, except that the The Agency for Toxic Substances and Disease Registry
proportion of lead-zinc-copper sulfides, such as chalcopyrite, (ATSDR) provides a useful summary of the human toxicology
galena, and sphalerite, is reduced relative to the gangue of aluminum (Agency for Toxic Substances and Disease
minerals (barite, calcite, dolomite, pyrite, and quartz) (Kelley Registry, 2008). Exposure to aluminum by the general public
and others, 1995; Leach, Viets, and others, 1995). Because of is most likely to occur through consumption of food, water,
their association with sulfides and secondary minerals, such and aluminum-bearing medicines (such as antacids or antidiar-
elements as Ag, Al, As, Au, B, Ba, Cd, Co, Fe, Ga, Ge, Hg, rheal agents). Occupational exposure to aluminum is most
Mn, Mo, Ni, and Sb can also be found in clastic-dominated likely to occur during ore processing and product fabrication.
deposits (Briskey, 1986; Kelley and others, 1995). Likewise, Most ingested or inhaled aluminum is not absorbed by the
Mississippi Valley-type deposits can contain minor to trace body, although absorption can vary depending upon the
amounts of Ag, As, Au, Ba, Bi, Cd, Co, Cu, F, Fe, Ga, Ge, In, chemical form and particle size. Overexposure to aluminum
Mo, Ni, Pb, Sb, Sn, and Tl (Leach, Viets, and others, 1995; can affect the nervous system, causing impaired performance
Foley, 2002a). Under oxidizing and acidic (pH < 3) weathering in motor, sensory, and cognitive function. In addition,
conditions, which would be expected in clastic-dominated aluminum workers may suffer respiratory effects, such as
mine waste having little to no acid-neutralizing capacity and impaired lung function and fibrosis. The United States national
significant pyrite content, many of these elements are mobile secondary drinking water regulation for aluminum, which
(Smith and Huyck, 1999). The acid-neutralizing capacity is a nonenforceable guideline, ranges from 50 to 200 µg/L
of carbonate-hosted mine waste is greater, however, and (U.S. Environmental Protection Agency, 2013b). Most surface
the oxidizing and circumneutral (5 < pH < 8) conditions that waters contain aluminum concentrations below 100 µg/L
prevail during weathering would cause most of the elements (Agency for Toxic Substances and Disease Registry, 2008).
listed above to be less mobile or immobile (Smith and Huyck, Mining of deposits where gallium is a byproduct can
1999). An important exception is zinc, which can make up a potentially mobilize elements that are known human toxins;
large percentage of the total dissolved metals draining from these elements have the potential to affect human health
Mississippi Valley-type deposits (Plumlee and others, 1999). when present above threshold concentrations in air, drinking
A review of the environmental geochemistry of platform water, and soils. These concentrations can be exceeded near
carbonate-hosted sulfide deposits identifies surface disposal mine sites. The best known examples are the neurological
of tailings as a potential environmental concern, especially effects of lead on children (Holecy and Mousavi, 2012) and
if As, Cd, Tl, and Zn are present, because airborne dust may the carcinogenic effects of arsenic in drinking water (Gupta
contain metal particulates (Foley, 2002a). A study of the and others, 2012). The current U.S. National Ambient Air
Austinville lead-zinc mine in Wythe County, Virginia (Foley, Quality Standard for lead is 0.15 micrograms per cubic meter
2002b), shows that residual soils near a Mississippi Valley- (U.S. Environmental Protection Agency, 2013a), and current
type deposit can be acidic enough to influence the mobility of U.S. primary and secondary drinking water standards for lead,
metals in surface environments and that this is especially true zinc, and copper are 0, 5, and 1 milligrams per liter (mg/L),
for Mississippi Valley-type deposits that have high jasperoid respectively (U.S. Environmental Protection Agency, 2013b).
and pyrite content. Canadian agricultural soil quality guidelines for lead, zinc,
and copper are 70, 200, and 63 mg/kg, respectively (Canadian
Council of Ministers of the Environment, 2007).
Human Health Concerns
Study of the health effects of gallium on humans largely Ecological Health Concerns
focuses on exposure to synthetic gallium arsenide (GaAs) by
workers in the semiconductor industry, where small GaAs Relatively few studies focus on the ecological effects of
particles can be inhaled or ingested (Flora, 2000). The toxicity gallium mobility in the environment. Fish tend to be sensitive to
of GaAs may result from the arsenic (because arsenic trioxide low concentrations of dissolved metals, and they are therefore
may be released from GaAs after absorption); gallium toxicity, useful indicators of contamination in aquatic systems. One
however, though not well studied, has not been ruled out of several useful endpoints used in toxicity tests is the lethal
(Chitambar, 2010). Humans can tolerate intravenous infusions concentration that leads to 50 percent mortality (LC50 )
of gallium nitrate during medical treatments for diseases after exposure to a substance for a certain amount of time.
Environmental Considerations H25
A study on the acute toxicity of dissolved gallium to carp Carbon Footprint

(Cyprinus carpio Linnaeus) revealed a mean LC50 value of
95.6 ± 14.3 mg/L after 96 hours of exposure (Betoulle and Gallium has potential application in the effort to reduce
others, 2002). Chronic toxicity tests with dissolved gallium the carbon footprint from energy production because of its use
and developing rainbow trout (Oncorhynchus mykiss) in efficient thin-film photovoltaic cells (solar panels) (Miles
revealed a mean LC50 value of 3.5 mg/L after 28 days of and others, 2007). The copper-indium-gallium-(di)selenide
exposure (Birge and others, 1980). In acute toxicity tests with (CIGS) alloy, among others, is an attractive thin-film product
saltwater organisms, LC50 values ranged from 12 to 55 mg/L because of its high efficiency and relatively low material
of gallium after 24, 48, or 96 hours of exposure (Onikura and and manufacturing costs (Kaneshiro and others, 2010). In
others, 2005). Gallium is typically not included in the suite a comparative study of lifecycle greenhouse gas emissions
of elemental concentrations reported in studies of mine waste for various technologies, Kim and others (2012) found that
water chemistry, so these LC50 values cannot be compared estimates for the carbon footprint of CIGS technologies under
with likely gallium concentrations in mining environments. test conditions are about 26 grams of CO2 equivalent per
The ecological effects of gallium may be similar to those kilowatthour (g CO2-equiv/kWh), which compares well with
of aluminum given their similar behavior in the environment. older technologies that have greenhouse gas emissions in the
When brown trout (Salmo trutta Linnaeus) were exposed to range of 39 to 110 g CO2-equiv/kWh (Fthenakis and others,
stream water samples of various pH levels and aluminum 2008). The CIGS photovoltaic cells are in the initial stages
concentrations, the healthiest populations were observed in of commercialization, but they are expected eventually to
waters with pH above 5.0 and aluminum concentrations below compete with other forms of energy production as economies
20 µg/L; significantly higher aluminum concentrations in gills of scale permit future cost reductions (Miles and others, 2007;
were observed in moribund fish, suggesting that complications Rockett, 2010). With the rapid evolution of the thin-film
with respiration contributed to their decline (Andrén and photovoltaic cell industry, the recyclability of generated
Rydin, 2012). In toxicity tests with tropical freshwater algal products and the potential for leaching of toxic elements from
and zooplankton species, LC50 values for aluminum increased improperly disposed products would need to be addressed.
with increasing dissolved organic carbon concentrations
(Trenfield and others, 2012), suggesting that the affinity of Mine Closure
aluminum for complexing with organic carbon renders it less
toxic. The National Ambient Water Quality Criteria recom- Most recent and new mining operations include closure
mended for the protection of aquatic life and adopted by some plans that address issues related to the mine footprint, which
regions in the United States are 750 micrograms of aluminum includes waste left onsite and locally affected soil and water,
per liter (µg Al/L) of water (acute) and 87 µg Al/L of water as well as ecological effects, such as habitat destruction and
(chronic) (Suter and Tsao, 1996). Because aluminum is more loss of biodiversity. Bauxite mines can be particularly prone
mobile under acidic conditions, plants growing in acidic soils to soil and habitat loss given that many are located in tropical,
may suffer from aluminum toxicity, which is known to inhibit biodiverse locations. A study of a 10-year-old reforested area
root growth and crop yields (Kabata-Pendias and Mukherjee, at a closed bauxite mine in Brazil showed that, although the
2007). As a result, some regions of the United States have reforestation program created adequate recovery conditions,
adopted a soil screening benchmark of 50 ppm of soil for recovery of native flora was influenced by the uneven return of
terrestrial plants, as recommended by Oak Ridge National important seed-dispersing animals (Parrotta and others, 1997).
Laboratory (Efroymson and others, 1997). At one of the largest bauxite mine operations in the State
The ecological effects of other elements that gallium is of Western Australia, Australia, the Alcoa World Alumina
associated with are relatively well documented. For example, Australia company clears the Jarrah (Eucalyptus marginata)
in toxicity tests with aquatic invertebrates incubated with forest before developing an open pit mine; after extracting
mine tailings from Mississippi Valley-type deposits, Besser bauxite, the company returns the topsoil and spreads Jarrah
and Rabeni (1987) showed that increased concentrations of seeds at a rate of approximately 550 hectares per year
dissolved cadmium, lead, and zinc correlated with decreased (Gardner and Bell, 2007).
survival and growth (Besser and Rabeni, 1987). Likewise, With respect to mining in zinc deposits, mine closure
various fish species experienced rapid mortality when exposed issues often relate to the stability of large waste piles and
to increasing dissolved zinc concentrations, but this effect tailings dams, and the potential for acid mine drainage from
decreased with increasing calcium, magnesium, and sodium the site. Mine waste pile stability is commonly addressed
concentrations (De Schamphelaere and Janssen, 2004). High through grading and covering dewatered piles. Acid mine
metal concentrations in soils can also cause phytotoxicity. drainage can be addressed with active water treatment
Zinc is a micronutrient for many plant species, but when facilities, passive limestone-lined channels, or constructed
highly concentrated in soils, it can inhibit a plant’s metabolic wetlands (Plumlee and Logsdon, 1999). The end result of both
functions and cause deficiencies in other essential nutrients, active and passive approaches is precipitation of dissolved
such as copper, iron, manganese, and phosphorus (Nagajyoti metals. Precipitated metals in reconstructed wetland systems
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whereas the metal-rich precipitates that result from active

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For more information concerning this report,
please contact:
Mineral Resources Program Coordinator
913 National Center
Reston, VA 20192
Telephone: 703– 648– 6100
Fax: 703– 648– 6057
Email: minerals@usgs.gov
Home page: https://minerals.usgs.gov
Prepared by the USGS Science Publishing Network

Reston Publishing Service Center
Edited by J.C. Ishee and Stokely J. Klasovsky
Illustrations by Caryl J. Wipperfurth
Layout by Caryl J. Wipperfurth and Cathy Y. Knutson
Posting by Angela E. Hall
Foley and others—Critical Mineral Resources of the United States—Gallium —Professional Paper 1802–H
https://doi.org/10.3133/pp1802H
ISSN 2330-7102 (online)

Gallium: Professional Paper 1802-H

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Gallium

Professional Paper 1802–H

U.S. Department of the Interior

lithium beryllium boron carbon nitrogen oxygen fluorine neon

sodium magnesium aluminum silicon phosphorus sulfur chlorine argon

89 90 91 92 93 94 95 96 97 98 99 100 101 102 103

element names in blue are liquids at room temperature

By Nora K. Foley, Brian W. Jaskula, Bryn E. Kimball, and Ruth F. Schulte

Professional Paper 1802– H

U.S. Department of the Interior

U.S. Geological Survey

U.S. Geological Survey, Reston, Virginia: 2017

ISSN 2330-7102 (online)

International System of Units to Inch/Pound—Continued

Inch/Pound to International System of Units

Concentration unit Equals

Metric system prefixes

Abbreviations and Symbols

By Nora K. Foley, Brian W. Jaskula, Bryn E. Kimball, and Ruth F. Schulte

Abstract imports of primary, recycled, and refined gallium, as well as

televisions, and desktop computer monitors. 30 31 32

charge, such as aluminum and zinc. For example, gallium 48 49 50

A. Estimated world primary gallium production

Primary production Refined production (includes

B. Estimated world primary gallium production capacity

China Other producers

C. U.S. gallium consumption U.S. gallium consumption by end use, 2012

180° 135° 90° 45° 0° 45° 90° 135° 180°

70° Red Dog Nanisivik

Figure H4. World map showing

A. Karst bauxite deposits B. Lateritic bauxite deposits

Bauxitic paleosol Lateritic

C. Sediment-hosted lead-zinc deposits D. Clastic-dominated-type lead-zinc deposits

Underlying rocks Metal extraction

EXPLANATION (part C ) EXPLANATION (part D )

Central Viburnum Northern

ALL FIGURES NOT TO SCALE

Mineralogy Namibia (Frimmel and others, 1996, and references therein).

≥30 ppm gallium

Table H3. Selected gallium-bearing minerals—Formula, content, and occurrence.

high concentrations (0.05 weight percent) in feldspars from Gibbsite-Diaspore-Boehmite

sulfide Maine, United States Bacon and others

to bornite-chalcopyrite-tennantite-galena-sphalerite ore of gallium in source materials. Factors controlling gallium

A study on the acute toxicity of dissolved gallium to carp Carbon Footprint

whereas the metal-rich precipitates that result from active

Prepared by the USGS Science Publishing Network

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