Gallium is a chemical element with the symbol Ga and atomic number 31, classified as a post-transition metal in group 13 of the periodic table.[1] It appears as a soft, silvery-white metal that melts at approximately 29.8 °C, just above room temperature, and boils at around 2,400 °C, with a density of about 5.9 g/cm³ in its solid form.[1] This low melting point, shared with only a few other metals like mercury, allows gallium to exist as a liquid under mild heating, and it is known for its toxicity upon ingestion and corrosiveness to aluminum.[1][2]Discovered in 1875 by French chemist Paul-Émile Lecoq de Boisbaudran through spectroscopic analysis of zinc extracted from the mineral sphalerite, gallium fulfilled a prediction made by Dmitri Mendeleev in 1871, who described it as "eka-aluminum" based on periodic table trends.[2] Gallium does not occur in its elemental form in nature but is present in trace amounts—typically 50 to 100 parts per million—in ores such as bauxite (aluminum ore) and sphalerite (zinc sulfide), from which it is recovered as a byproduct during the processing of aluminum and zinc.[1][2] Global reserves are estimated to exceed 1 billion kilograms, primarily in bauxite deposits, though production is concentrated in countries like China, which accounts for a significant share of the world's output of around 320,000 kilograms of high-purity gallium annually as of 2024.[3][4]The element's primary applications stem from its semiconducting compounds, with ~83% of U.S. consumption in the form of gallium arsenide (GaAs), gallium nitride (GaN), and gallium phosphide (GaP) for use in integrated circuits, light-emitting diodes (LEDs), laser diodes, solar cells, and optoelectronic devices essential to smartphones, data networks, and clean energy technologies.[3][2] About 79% of gallium use goes into integrated circuits, while the remainder supports epitaxial layers for advanced wafers and niche applications like high-temperature thermometers, low-melting alloys, and research in photovoltaics.[3] The U.S. relies entirely on imports for gallium, sourcing it mainly from Canada, China, Germany, and Japan, highlighting its status as a critical mineral for modern electronics and national security as of 2025.[3][5]
Physical properties
General characteristics
Gallium is a silvery-white, soft metal that exhibits a notably low melting point of 29.76 °C (85.57 °F), enabling it to liquefy upon contact with human skin at typical body temperature. Its density measures 5.91 g/cm³ at 20 °C, and unlike most substances, it undergoes a volume expansion of approximately 3.2% during solidification, which can pose challenges for storage in rigid containers. The element adopts an orthorhombic crystal structure with 8 atoms per unit cell in its stable α-phase at standard conditions. While gallium displays brittleness at low temperatures, such as below 0 °C, it becomes malleable in its solid form near room temperature.[1][6][7]Thermodynamically, gallium possesses a high boiling point of 2403 °C (4357 °F), contributing to its wide liquid range spanning over 2370 °C.[8] The standard enthalpy of formation for elemental gallium is 0 kJ/mol, as defined for elements in their standard state. Its specific heat capacity is 0.371 J/g·K, reflecting moderate thermal absorption, while the thermal conductivity stands at 40.6 W/m·K, indicating decent but not exceptional heat transfer compared to common metals like copper.[2][1][9]Electrically, gallium exhibits a resistivity of $27.3 \times 10^{-8} Ω·m at 20 °C, classifying it as a relatively poor conductor among metals, with conductivity roughly one-sixth that of silver. Optically, pure gallium presents a shiny, reflective surface, but it readily tarnishes in moist air to develop a thin oxide layer, imparting a duller appearance over time.[9][10]
Isotopes
Gallium has two stable isotopes: ^{69}\mathrm{Ga} with a natural abundance of 60.108(9)% and ^{71}\mathrm{Ga} with 39.892(9)% abundance.[11] These isotopes contribute to the standard atomic weight of gallium, which is 69.723(1) u.[11] Both stable isotopes have a nuclear spin of $3/2 and negative parity ($3/2^-).[12][13]A total of 33 isotopes of gallium are known, spanning mass numbers from 56 to 88.[14] Only the pair ^{69}\mathrm{Ga} and ^{71}\mathrm{Ga} are stable, rendering gallium effectively monoisotopic in natural samples despite the existence of synthetic variants. All other isotopes are radioactive, with no long-lived radioisotopes; the longest half-life among them is that of ^{67}\mathrm{Ga} at 3.2617 days, which decays primarily by electron capture.[15] Another notable radioactive isotope is ^{68}\mathrm{Ga}, with a half-life of 67.83(20) minutes, also decaying by electron capture and used in medical applications due to its positron emission properties.[16]The stable gallium isotopes exhibit neutron capture cross-sections relevant to nuclear reactor applications. The thermal neutron capture cross-section for ^{69}\mathrm{Ga} is approximately 1.69(8) barns, while for ^{71}\mathrm{Ga} it is about 4.05(27) barns.[17][18] These values influence gallium's behavior in neutron flux environments, such as in activation analysis or reactor materials.
Chemical properties
Aqueous chemistry
Gallium(III) ions (Ga³⁺) exhibit high solubility in water, primarily existing as the hexaaqua species [Ga(H₂O)₆]³⁺ in acidic conditions.[19] However, these ions undergo rapid hydrolysis even at low pH, leading to the formation of hydroxo complexes.[20]The hydrolysis of Ga³⁺ proceeds stepwise, beginning with the dissociation:[\mathrm{Ga(H_2O)_6}]^{3+} \rightleftharpoons [\mathrm{Ga(H_2O)_5OH}]^{2+} + \mathrm{H}^+with a first acidity constant \mathrm{p}K_{a1} = 2.85 at 25°C and zero ionic strength.[20] Subsequent steps involve further deprotonation, culminating in the precipitation of gallium(III) hydroxide, Ga(OH)₃, as an amorphous or crystalline solid when the pH exceeds approximately 3.[21] This precipitation reflects the low solubility of Ga(OH)₃ across a broad pH range from 3 to 8 at 25°C, limiting the mobility of gallium in neutral aqueous environments.[21]Gallium(III) hydroxide displays amphoteric behavior, dissolving in strong alkaline solutions to form tetrahydroxogallate ions, [Ga(OH)₄]⁻, which facilitates its solubility in basic media.[22] Ga³⁺ also forms stable coordination complexes with various ligands in aqueous solution; for example, the stability constant for the Ga³⁺-EDTA complex is \log \beta = 22.1 at 25°C and ionic strength 0.1 M, indicating strong chelation suitable for analytical and radiochemical applications.[23] Similarly, Ga³⁺ binds to citrate, forming multiple hydroxo-citrate species, which influences gallium speciation in biological fluids.[24]The redox behavior of gallium in aqueous solution is characterized by the standard reduction potential for the Ga³⁺/Ga couple, E^\circ = -0.56 V vs. SHE, which underscores the thermodynamic stability of Ga³⁺ relative to metallic gallium under standard conditions.[25] This potential contributes to the inertness of gallium metal toward oxidation in air, as a passivating oxide layer forms on the surface, preventing further reaction even in moist environments.[19]
Binary compounds
Gallium forms a variety of binary compounds with non-metals, primarily through high-temperature reactions involving direct combination of the elements, such as the oxidation of gallium metal to gallium(III) oxide via $4\text{Ga} + 3\text{O}_2 \rightarrow 2\text{Ga}_2\text{O}_3.[26] These compounds exhibit diverse structures and properties, ranging from wide-bandgap insulators to semiconductors, and the halides are notable for their volatility, which facilitates purification processes through sublimation or distillation.[26]The oxides of gallium are dominated by gallium(III) oxide, \text{Ga}_2\text{O}_3, which exists in multiple polymorphs, including the thermodynamically stable monoclinic \beta-form and the corundum-type \alpha-form. The \beta-\text{Ga}_2\text{O}_3 polymorph features a wide indirect bandgap of approximately 4.8 eV, making it a promising ultrawide-bandgap semiconductor, while the \alpha-form has a slightly larger bandgap ranging from 4.9 to 5.6 eV.[27][28] Synthesis of these oxides typically occurs via thermal oxidation of gallium or decomposition of gallium salts at elevated temperatures above 600°C.[29]Gallium chalcogenides, such as gallium monosulfide (\text{GaS}), monogallium selenide (\text{GaSe}), and monogallium telluride (\text{GaTe}), adopt layered crystal structures with weak van der Waals interactions between layers, enabling exfoliation into two-dimensional forms. These materials are indirect-bandgap semiconductors with bandgaps decreasing from about 2.5 eV for \text{GaS} to 1.3 eV for \text{GaTe}, and they are synthesized by direct reaction of gallium with the chalcogen elements at high temperatures around 700–900°C.[30][31]Among the pnictides, gallium nitride (\text{GaN}) crystallizes in the wurtzite structure and possesses a direct bandgap of 3.4 eV, contributing to its utility in optoelectronic devices like light-emitting diodes through efficient electron-hole recombination.[32] The other gallium pnictides—gallium phosphide (\text{GaP}), gallium arsenide (\text{GaAs}), and gallium antimonide (\text{GaSb})—adopt the zincblende structure, with indirect bandgaps for \text{GaP} at 2.26 eV, direct for \text{GaAs} at 1.42 eV, and direct for \text{GaSb} at 0.67 eV, reflecting a trend of decreasing bandgap with increasing atomic number of the pnictogen.[33] These pnictides are prepared by high-temperature reactions, often under controlled atmospheres to prevent oxidation, such as reacting gallium with phosphine or arsine vapors.[34]The gallium trihalides include \text{GaCl}_3, \text{GaBr}_3, and \text{GaI}_3, which are covalent Lewis acids that form dimeric structures in the gas phase due to bridging halide ligands, enhancing their volatility for applications like chemical vapor deposition.[26] In contrast, gallium trifluoride (\text{GaF}_3) exhibits more ionic character with a polymeric rutile-like structure in the solid state and a high melting point of 800°C, resulting from strong Ga–F bonds.[26] These halides are synthesized by direct halogenation of gallium at moderate temperatures (200–400°C) and serve as precursors in various synthetic routes owing to their Lewis acidity.[26]Binary gallium hydrides are limited, with gallium trihydride (\text{GaH}_3) being polymeric and highly unstable, decomposing above –30°C to elemental gallium and hydrogen gas, unlike the more stable borane analogs.[35] No persistent binary gallium hydride exists under standard conditions, and attempts to isolate \text{GaH}_3 typically involve low-temperature stabilization with ligands or solvents, followed by rapid decomposition.[35]
Organogallium compounds
Organogallium compounds encompass a diverse class of organometallic species characterized by gallium-carbon bonds, which exhibit distinctive reactivity arising from the Lewis acidity of trivalent gallium and its tendency to form oligomeric structures. These compounds are pivotal in synthetic organometallic chemistry, serving as versatile reagents and precursors for advanced materials. Key subclasses include alkylgalliums, arylgalliums, and gallium alkoxides, each displaying unique structural and reactive profiles influenced by steric and electronic factors.[36]Alkylgallium compounds, such as trimethylgallium \left( (CH_3)_3Ga \right), adopt a tetrahedral geometry around the gallium center and are colorless, volatile liquids that are highly pyrophoric, igniting spontaneously in air due to their strong reducing nature. Aryl derivatives, like triphenylgallium \left( (C_6H_5)_3Ga \right), feature more stable gallium-aryl bonds owing to conjugation effects, often forming dimeric structures in the solid state. Gallium alkoxides, represented by formulas such as [Ga(OR)_3]_n (where R is alkyl or aryl and n denotes oligomerization), typically oligomerize through μ-oxo bridges, with monomeric forms stabilized by bulky substituents to prevent aggregation.[36]Synthesis of these compounds commonly proceeds via salt metathesis reactions involving gallium halides and organometallic reagents. For instance, trimethylgallium is prepared by treating gallium trichloride with methyllithium in a hydrocarbon solvent: GaCl_3 + 3 CH_3Li \to (CH_3)_3Ga + 3 LiCl. Similar approaches apply to arylgalliums using aryllithium reagents, while gallium alkoxides are accessed through alcoholysis of alkylgalliums, such as GaR_3 + 3 R'OH \to Ga(OR')_3 + 3 RH, or by reacting gallium halides with alkali metal alkoxides. These methods yield high-purity products suitable for sensitive applications, often under inert atmospheres to mitigate reactivity.[36]The reactivity of organogallium compounds stems from their air and moisture sensitivity, leading to rapid hydrolysis and formation of gallium oxides or hydroxides. Alkyl variants prone to β-hydride elimination, particularly those with β-hydrogens in the alkyl chain, undergo decomposition to alkenes and gallium hydrides, a process exacerbated at elevated temperatures. The inherent Lewis acidity of the gallium center enables coordination to Lewis bases, facilitating catalytic roles in alkyne activation and nucleophilic additions. In catalytic applications, organogalliums participate in Ziegler-Natta-like polymerizations of olefins, where they promote chain growth through alkyl group transfer, albeit less efficiently than aluminum analogs due to weaker metal-carbon bonds.[36][37]Organogalliums find prominent use as precursors in chemical vapor deposition (CVD) for gallium nitride (GaN) semiconductors, with trimethylgallium reacting under ammonia to deposit high-quality films essential for optoelectronics. Gallium alkoxides serve as volatile precursors for gallium oxide (Ga₂O₃) thin films in gas sensors. Stability metrics underscore their handling challenges: the gallium-carbon bond dissociation energy in trimethylgallium is approximately 250 kJ/mol, reflecting moderate strength compared to aluminum analogs, while thermal decomposition typically occurs above 400°C under inert conditions, yielding metallic gallium and hydrocarbons.[38][36]
History and occurrence
History
In 1871, Russian chemist Dmitri Mendeleev predicted the existence of an undiscovered element positioned below aluminum in his periodic table, designating it "eka-aluminum" and anticipating key properties including a density of approximately 6.0 g/cm³ and a low melting point, based on periodic trends among analogous elements.[39] These predictions stemmed from gaps in the table and extrapolations from known group 13 elements like aluminum and indium.The element was discovered four years later in 1875 by French chemist Paul-Émile Lecoq de Boisbaudran, who identified it through spectroscopic analysis of residues from zinc blende (sphalerite) ore, observing two prominent violet spectral lines indicative of a new metal.[40] Lecoq de Boisbaudran named the element gallium after "Gallia," the Latin term for France, honoring his homeland. In late 1875, he isolated small quantities of the metal via electrolysis of a gallium hydroxide solution, and by 1876, he had produced about 75 grams for further study.[41]Early measurements confirmed Mendeleev's predictions remarkably well: gallium's density was determined to be 5.9 g/cm³ (after initial reports of 4.7 g/cm³ were revised), and its melting point was found to be 29.8 °C, aligning closely with the foreseen low-melting, aluminum-like characteristics.[39] This validation bolstered confidence in Mendeleev's periodic system. In 1926, Norwegian geochemist Victor Goldschmidt synthesized gallium arsenide, the first compound to reveal gallium's potential semiconductor properties due to its electronic structure.[42]Post-World War II advancements in the 1950s, driven by the burgeoning electronics industry, included zone refining and distillation techniques that achieved ultra-high purity gallium (up to 99.9999%), essential for doping semiconductors and enabling applications in transistors and early integrated circuits.[43] These purification methods, pioneered in laboratories like those at Siemens, marked gallium's transition from a chemical curiosity to a critical material in solid-state technology.[44]
Occurrence
Gallium is a trace element in the Earth's crust with an average abundance of less than 19 parts per million (ppm), making it relatively common among metals despite its limited economic concentrations.[9] In soils, gallium concentrations typically range from 5 to 50 ppm, varying with parent rock composition and weathering processes.[9] This distribution reflects gallium's geochemical compatibility with aluminum- and iron-bearing phases during crustal differentiation.The primary natural sources of gallium are associated with aluminum and zinc ores, as well as certain industrial byproducts. Bauxite, the principal ore of aluminum, contains gallium at concentrations averaging 57 ppm, with values up to 146 ppm (0.015%) in some deposits.[45] In zinc ores, gallium is primarily hosted in sphalerite, where it averages around 26 ppm in representative deposits like those at the Red Dog Mine, Alaska, though levels can exceed 300 ppm in enriched zones.[9] Coal fly ash, derived from combustion of gallium-bearing coals, often concentrates the element to 30–100 ppm or higher, up to 0.1% in exceptional cases.[46]Gallium rarely occurs as a native metal and is instead found in trace amounts within specific minerals and as a substituent in common rock-forming phases. Notable gallium minerals include gallite (CuGaS₂), a sulfide found in copper-zinc deposits such as those at Kipushi, Democratic Republic of Congo.[47] Other rare phases, like gallobeudantite [PbGa₃(AsO₄)(SO₄)(OH)₆], occur in oxidized zones of polymetallic deposits.[48] More commonly, gallium substitutes for Al³⁺ or Fe³⁺ in silicate structures, such as kaolinite (Al₂Si₂O₅(OH)₄), where it can comprise up to several percent of the octahedral sites in aluminum-rich clays.[9]Geochemically, gallium displays a chalcophile affinity, favoring association with sulfur in sulfide minerals like sphalerite and chalcopyrite during hydrothermal ore formation.[9] This behavior leads to its enrichment in sedimentary environments influenced by organic matter, where it can show biophilic tendencies in certain biogenic sediments.[49]
Production and supply
Production methods
Gallium is primarily extracted as a byproduct of alumina production from bauxite ore through the Bayer process. In this process, bauxite is digested with sodium hydroxide to form sodium aluminate liquor, in which gallium co-precipitates alongside aluminum. The gallium-rich liquor is then subjected to electrolytic recovery, typically using a mercury or aluminum cathode to deposit gallium metal at the bottom of the electrolysis cell, achieving yields of approximately 90%.[50][51]Secondary sources contribute significantly to gallium supply, particularly from zinc smelting operations. During the hydrometallurgical processing of sphalerite (zinc sulfide ore), gallium reports to the leachate solutions; it is subsequently recovered via solvent extraction or electrowinning from these zinc plant residues, with extraction efficiencies exceeding 90% in optimized systems. Additionally, gallium can be leached from coal fly ash using sulfuric acid, followed by impurity removal and solvent extraction, though this method remains less commercialized compared to bauxite and zinc routes.[52][53]Refining of crude gallium involves multiple steps to achieve high purity levels required for applications like semiconductors. Crude gallium is often converted to gallium chloride (GaCl₃) and purified by fractional distillation under reduced pressure, removing volatile impurities. Further purification employs zone refining, where a molten zone is passed along a gallium ingot to segregate impurities to one end, yielding ultra-high purity grades of 99.99999% (7N). Global production of high-purity refined gallium reached approximately 320 tonnes in 2024.[54][55][4]The overall production process is energy-intensive, with primary extraction and refining consuming around 100 kWh per kilogram of gallium, primarily due to electrolysis and purification steps. Recycling from end-of-life semiconductors and electronics recovers an estimated 10-20% of global supply, involving hydrometallurgical leaching and re-refining to supplement primary output.[56][57]
Availability and market dynamics
China's dominance in gallium production has profoundly shaped global supply dynamics, with the country accounting for 99% of low-purity gallium output in 2024.[4] This concentration stems from gallium's status as a byproduct of aluminum and zinc refining, where China leads in both sectors, producing an estimated 750 tonnes annually from these processes.[4] To mitigate risks, diversification efforts are underway; in May 2025, Rio Tinto and Indium Corporation initiated a pilot-scale primary gallium extraction project at Rio Tinto's Vaudreuil alumina refinery in Quebec, Canada, with plans for a commercial plant targeting an annual capacity of approximately 40 tonnes, scalable to higher volumes.[58] This North American venture represents a critical step toward reducing reliance on Asian supply chains.Geopolitical tensions have further disrupted availability, particularly through China's export restrictions implemented in July 2023 amid the U.S.-China "chip war" over advanced semiconductor technologies.[59] The controls halted shipments of gallium and related products to the U.S., causing global prices to surge from about $200-250 per kilogram in 2022 to averages over $500 per kilogram by 2024, with peaks of approximately $550-600 per kilogram in early 2024 due to stockpiling and supply shortages.[4][60][61] However, on November 11, 2025, China suspended these export restrictions on gallium (along with germanium and antimony) to the U.S. until November 27, 2026, providing temporary relief to international supply chains.[62] These measures not only strained international trade but also prompted Western nations to accelerate domestic sourcing and stockpiling strategies.Global gallium resources, primarily embedded in bauxite and zinc ores, are estimated to exceed 1 million tonnes, though less than 10% (under 100,000 tonnes) is potentially economically recoverable.[4] Recycling from electronic waste offers supplementary potential, with estimates suggesting 20-30% recovery rates feasible through advanced processes like hydrometallurgical leaching from GaAs and GaN scraps, though current end-of-life recycling remains below 1%.[63]Market trends reflect robust demand growth of approximately 6.5% annually, fueled by electronics applications in 5G infrastructure, LEDs, and power devices, projecting consumption to reach around 750 tonnes by 2030.[64] The U.S. Geological Survey highlights supply vulnerabilities from China's market control, estimating potential U.S. GDP losses of up to $3.4 billion under full export bans, underscoring the need for diversified sourcing and recycling to stabilize prices and availability.[65]
Applications
Semiconductors and electronics
Gallium plays a pivotal role in semiconductor materials, particularly in compound semiconductors like gallium arsenide (GaAs) and gallium nitride (GaN), which enable high-performance electronic devices due to their superior electrical and optical properties. GaAs, a III-V compound, features a direct bandgap of 1.42 eV and high electron mobility of approximately 8500 cm²/V·s at room temperature, making it ideal for applications requiring rapid electron transport.[66] These characteristics allow GaAs to excel in radiofrequency (RF) amplifiers, where it supports high-frequency operations in wireless communication systems.[67]GaN, another key gallium-based material, possesses a wider direct bandgap of 3.4 eV, enabling operation at higher voltages and temperatures while maintaining efficiency in optoelectronic devices.[68] This property positions GaN as essential for high-power light-emitting diodes (LEDs) and laser diodes, which are widely used in solid-state lighting, displays, and optical data storage.[69] In device applications, gallium compounds power high-electron-mobility transistors (HEMTs), particularly GaN-based variants that deliver high power density and efficiency for 5G base stations and radar systems.[70] GaN is increasingly used in power electronics for electric vehicles and renewable energy systems, supporting higher efficiency in 5G and emerging 6G networks as of 2025. Multi-junction solar cells incorporating GaInP/GaAs structures achieve efficiencies exceeding 40% under concentrated sunlight, setting records for photovoltaic performance in space and terrestrial concentrator systems.[71] Additionally, GaAs supports integrated circuits (ICs) for microwave and high-speed digital applications, offering advantages over silicon in frequency response and power handling.[72]The advantages of these gallium compounds stem from their direct bandgaps, which facilitate efficient light emission and absorption in optoelectronics, unlike silicon's indirect bandgap.[73] GaAs and GaN also exhibit greater thermal stability than silicon, with wider bandgaps allowing reliable operation at elevated temperatures up to several hundred degrees Celsius without significant performance degradation.[74] According to the U.S. Geological Survey's 2025 Mineral Commodity Summary (data for 2024), nearly all domestic gallium consumption—approximately 99%—is directed toward semiconductor applications, including ICs (79%) and optoelectronic devices (20%).[4] Epitaxial growth techniques, such as metal-organic chemical vapor deposition (MOCVD), are the primary methods for producing high-quality GaAs and GaN layers, enabling precise control over thickness and composition for advanced device fabrication.[75]
Alloys and metals
Gallium forms several low-melting-point metallic alloys valued for their fluidity and conductivity in mechanical and thermal applications. The most prominent is Galinstan, a eutectic alloy composed of 68.5 wt% gallium, 21.5 wt% indium, and 10 wt% tin, which melts at -19 °C and remains liquid well below room temperature.[76] This composition positions Galinstan as a non-toxic, environmentally safer alternative to mercury in applications requiring liquid metals, such as switches and thermal fluids.[77] Its density of 6.44 g/cm³ and electrical conductivity of approximately 3.46 × 10^6 S/m enable efficient current carrying and heat dissipation in confined spaces.[76]Galinstan exhibits a high surface tension of 624 mN/m, which contributes to its stability as droplets or wires, alongside good biocompatibility that minimizes adverse reactions in contact with biological tissues.[76] These properties support its use in flexible electronics, where it serves as a stretchable conductor in soft circuits and sensors that withstand deformation without breaking.[76] In heat transfer, Galinstan enhances cooling efficiency in microfluidic systems by filling microchannels and promoting rapid thermal conduction due to its low viscosity and metallic properties.[78]Preparation of Galinstan typically involves direct melting of the constituent metals under an inert atmosphere, such as argon or nitrogen, to prevent gallium's rapid oxidation and ensure a homogeneous eutectic mixture.[79] Other gallium alloys, including Ga-Pb and Ga-Al systems, are employed as solders in microelectronic interconnects, leveraging their low melting points and ability to form reliable bonds at reduced temperatures.[80] However, gallium's interaction with structural metals can lead to liquid metal embrittlement in steel and aluminum, where penetration along grain boundaries significantly reduces ductility and promotes brittle fracture.[81]
Biomedical uses
Gallium plays a significant role in biomedical applications, particularly in diagnostic imaging and therapeutic interventions for cancer and related conditions. In nuclear medicine, radiogallium isotopes are employed for detecting tumors and inflammatory processes. ⁶⁷Ga-citrate, administered intravenously, is used in single-photon emission computed tomography (SPECT) imaging to identify malignancies such as lymphomas and sarcomas, as well as sites of infection or inflammation, due to its accumulation in areas of increased metabolic activity and iron uptake.[82] This isotope has a physical half-life of 3.26 days (78 hours), allowing for imaging up to several days post-injection, with principal gamma emissions at 93 keV, 185 keV, and 300 keV facilitating detection.[83] Similarly, ⁶⁸Ga-DOTATATE is a positron emission tomography (PET) tracer targeting somatostatin receptors overexpressed in neuroendocrine tumors, enabling precise localization of primary and metastatic lesions with high sensitivity.[84] Its short half-life of 68 minutes supports rapid imaging protocols, and it is produced on-site via generators for clinical use.[85]In therapeutics, gallium compounds exploit their structural similarity to iron to interfere with cellular processes in diseased tissues. Gallium nitrate is approved by the U.S. Food and Drug Administration (FDA) for treating cancer-associated hypercalcemia refractory to hydration, where it inhibits osteoclastic bone resorption by disrupting iron-dependent enzymes in osteoclasts, thereby reducing serum calcium levels.[86] Administered intravenously at doses of 200 mg/m² daily for five days, it normalizes calcium in approximately 75% of patients, with effects lasting up to two weeks.[87] Another compound, gallium maltolate, an oral iron mimetic, targets dysregulated iron metabolism in cancer cells by binding to transferrin receptors and inhibiting iron-dependent pathways, showing preclinical efficacy against various solid tumors including glioblastoma.[88] Clinical trials of gallium maltolate in recurrent glioblastoma have demonstrated tolerability and preliminary antitumor activity, with ongoing phase I studies evaluating its safety at doses up to 300 mg daily.[89]Emerging applications leverage gallium's antimicrobial properties and nanoparticle formulations for advanced treatments. Gallium ions disrupt bacterial iron acquisition, exhibiting broad-spectrum activity against pathogens like Pseudomonas aeruginosa and Staphylococcus aureus in chronic wounds, and have been incorporated into hydrogel dressings for sustained release, promoting healing while minimizing resistance development.[90] In targeted drug delivery, gallium-based nanoparticles, such as those encapsulated in glucan particles, enhance macrophage-specific uptake and inhibit intracellular infections like HIV or mycobacteria, with sustained release extending efficacy for up to 15 days in preclinical models.[91]The FDA has approved specific gallium salts, including gallium nitrate for hypercalcemia and ⁶⁸Ga-gozetotide for prostate cancer imaging, underscoring their established roles in clinical practice.[92][93]
Other applications
Gallium-promoted ZSM-5 zeolites serve as additives in fluid catalytic cracking (FCC) units for hydrocarbon processing, facilitating the conversion of light alkanes to aromatics and olefins, which enhances gasoline octane quality.[94] These catalysts improve octane numbers by 5-10% through selective aromatization and cracking reactions.[95]In optical applications, gallium-indium alloys form liquid mirrors for astronomical telescopes, where the metal's low toxicity and reflectivity enable the creation of large parabolic surfaces via centrifugal rotation, offering a safer alternative to mercury-based systems.[96] Gallium-based restorative alloys also provide a mercury-free option for dental fillings, mimicking the properties of traditional amalgam while reducing health risks associated with mercury exposure.[97]Gallium functions as a dopant in semiconductor materials, such as germanium, to achieve superconductivity at temperatures up to 3.5 K, enabling research into quantum devices and low-temperature electronics.[98] Additionally, gallium nitride (GaN) is employed in neutron detectors, leveraging its wide bandgap (3.4 eV) and radiation resistance for efficient thermal neutron scintillation without conversion layers.[99]Niche uses include gallium-indium alloys in thermometers, where the liquid metal's expansion properties allow accurate temperature measurement up to 220°C as a non-toxic mercury substitute.[100] Gallium oxide (Ga₂O₃) is investigated for radiation detectors, particularly for X-ray and high-energy particle sensing, due to its ultrawide bandgap and scintillation efficiency.[101] In the U.S., these miscellaneous applications accounted for approximately 1% of gallium consumption as of 2024 data.[4]
Safety, health, and environmental aspects
Health and safety precautions
Gallium and its compounds pose health risks primarily through direct contact, inhalation, and ingestion, though overall toxicity is considered low compared to many heavy metals. The trivalent gallium ion (Ga³⁺) acts as an irritant, causing severe skin and eye irritation upon contact, potentially leading to burns or corneal damage with prolonged exposure.[102] Oral exposure to gallium metal exhibits low acute toxicity, with an LD50 greater than 2,000 mg/kg in rats (OECD Test Guideline 401), indicating it is not highly poisonous when swallowed in small amounts.[103] Inhalation of gallium fumes or dust can irritate the respiratory tract, resulting in coughing, wheezing, and shortness of breath; in cases involving gallium compounds like nitrates, this may progress to acute pulmonary edema or chemical pneumonitis.[102][104] Gallium metal and most compounds are not classified as carcinogenic by the International Agency for Research on Cancer (IARC Group 3: not classifiable as to carcinogenicity to humans).[105]Certain gallium derivatives present specific hazards beyond the elemental form. Organogallium compounds, such as trimethylgallium, are pyrophoric and can ignite spontaneously upon exposure to air, posing fire and explosion risks during handling. Radioisotopes like gallium-67 and gallium-68, used in medical imaging, emit ionizing radiation that can cause cellular damage, increasing risks of nausea, allergic reactions, and long-term carcinogenic effects with improper handling; occupational exposure must adhere to ALARA (As Low As Reasonably Achievable) principles.[106] Cases of gallium poisoning are rare but have been documented, including acute intoxication from accidental laboratory exposure leading to gastrointestinal distress and neurological symptoms.[107]Safe handling requires strict precautions to mitigate these risks. Operations involving gallium or its vapors should be conducted in a chemical fume hood to prevent inhalation, with personal protective equipment (PPE) including chemical-resistant gloves (such as nitrile), safety goggles, and lab coats mandatory to avoid skin and eye contact.[108] Gallium metal should be stored in tightly closed containers in a cool, dry place away from oxidizers, while pyrophoric organogallium compounds require storage under an inert atmosphere like nitrogen or argon to prevent ignition.[102] No specific OSHA permissible exposure limit (PEL) exists for gallium metal, but for related compounds like gallium arsenide, the PEL is 0.005 mg/m³ (as arsenic) over an 8-hour shift; general ventilation and monitoring are recommended to keep exposures below nuisance dust levels.[102][109] In contrast to industrial risks, therapeutic doses of stable or radioactive gallium in biomedical applications are carefully controlled to minimize adverse effects.[106]
Environmental distribution
Gallium occurs in trace amounts in the marine environment, primarily as dissolved species in seawater. Dissolved concentrations typically range from 5 to 40 pmol/kg as of 2021, with surface waters showing values of 5–43 pmol/kg due to scavenging by particulate matter.[110] The vertical profile exhibits a minimum at mid-depths and gradual enrichment toward deeper waters and the sediment-water interface, reflecting removal processes in the upper ocean and conservative behavior in deep waters, with surface values influenced by inputs and scavenging.[110]The primary sources of gallium to the oceans are riverine inputs and atmospheric deposition, contributing a combined global flux of approximately 10^4 tonnes per year, including both dissolved and particulate forms.[110] Sinks include particle scavenging and sedimentation, with limited bioaccumulation in marine organisms, where concentrations are generally below 1 ppm, indicating gallium is not an essential nutrient.[110]In geochemical cycling, gallium strongly adsorbs to iron and manganese oxides, facilitating its removal from solution and incorporation into sediments.[110] This process leads to significant enrichment in ferromanganese nodules, where concentrations can reach up to 300 ppm, particularly in regions influenced by volcanic inputs.[111]Recent studies since 2021 have investigated anthropogenic contributions, including potential leaching from electronic waste into aquatic systems, raising concerns about elevated trace metal inputs to coastal and oceanic environments. As of 2025, increasing recycling efforts from e-waste aim to recover gallium and mitigate these risks.[112][113]