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Mercury (element)
Mercury (element)
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Mercury, 80Hg
Mercury
Appearanceshiny, silvery liquid
Standard atomic weight Ar°(Hg)
Mercury in the periodic table
Hydrogen Helium
Lithium Beryllium Boron Carbon Nitrogen Oxygen Fluorine Neon
Sodium Magnesium Aluminium Silicon Phosphorus Sulfur Chlorine Argon
Potassium Calcium Scandium Titanium Vanadium Chromium Manganese Iron Cobalt Nickel Copper Zinc Gallium Germanium Arsenic Selenium Bromine Krypton
Rubidium Strontium Yttrium Zirconium Niobium Molybdenum Technetium Ruthenium Rhodium Palladium Silver Cadmium Indium Tin Antimony Tellurium Iodine Xenon
Caesium Barium Lanthanum Cerium Praseodymium Neodymium Promethium Samarium Europium Gadolinium Terbium Dysprosium Holmium Erbium Thulium Ytterbium Lutetium Hafnium Tantalum Tungsten Rhenium Osmium Iridium Platinum Gold Mercury (element) Thallium Lead Bismuth Polonium Astatine Radon
Francium Radium Actinium Thorium Protactinium Uranium Neptunium Plutonium Americium Curium Berkelium Californium Einsteinium Fermium Mendelevium Nobelium Lawrencium Rutherfordium Dubnium Seaborgium Bohrium Hassium Meitnerium Darmstadtium Roentgenium Copernicium Nihonium Flerovium Moscovium Livermorium Tennessine Oganesson
Cd

Hg

Cn
goldmercurythallium
Atomic number (Z)80
Groupgroup 12
Periodperiod 6
Block  d-block
Electron configuration[Xe] 4f14 5d10 6s2
Electrons per shell2, 8, 18, 32, 18, 2
Physical properties
Phase at STPliquid
Melting point234.3210 K ​(−38.8290 °C, ​−37.8922 °F)
Boiling point629.88 K ​(356.73 °C, ​674.11 °F)
Density (near r.t.)13.546 g/cm3[3]
Triple point234.3156 K, ​1.65 × 10−7 kPa
Critical point1750 K, 172.00 MPa
Heat of fusion2.29 kJ/mol
Heat of vaporization59.11 kJ/mol
Molar heat capacity27.983 J/(mol·K)
Vapor pressure[4]
P (Pa) 1 10 100 1 k 10 k 100 k
at T (K) 315 350 393 449 523 629
Atomic properties
Oxidation statescommon: +1, +2
−2[5]
ElectronegativityPauling scale: 2.00
Ionization energies
  • 1st: 1007.1 kJ/mol
  • 2nd: 1810 kJ/mol
  • 3rd: 3300 kJ/mol
Atomic radiusempirical: 151 pm
Covalent radius132±5 pm
Van der Waals radius155 pm
Color lines in a spectral range
Spectral lines of mercury
Other properties
Natural occurrenceprimordial
Crystal structurerhombohedral (hR1)
Lattice constants
Rhombohedral crystal structure for mercury
ar = 301.06 pm
α = 70.529°
ah = 347.64 pm
ch = 673.20 pm (at triple point)[6]
Thermal expansion60.4 µm/(m⋅K) (at 25 °C)
Thermal conductivity8.30 W/(m⋅K)
Electrical resistivity961 nΩ⋅m (at 25 °C)
Magnetic orderingdiamagnetic[7]
Molar magnetic susceptibility−33.44×10−6 cm3/mol (293 K)[8]
Speed of soundliquid: 1451.4 m/s (at 20 °C)
CAS Number7439-97-6
History
Namingfrom the planet Mercury, with which it was associated in medieval alchemy
DiscoveryAncient Egyptians (before 1500 BCE)
Symbol"Hg": from its Latin name hydrargyrum, itself from Greek hydrárgyros, 'water-silver'
Isotopes of mercury
Main isotopes[9] Decay
Isotope abun­dance half-life (t1/2) mode pro­duct
194Hg synth 447 y ε 194Au
195Hg synth 10.7 h β+ 195Au
196Hg 0.15% stable
197Hg synth 64.14 h ε 197Au
198Hg 10.0% stable
199Hg 16.9% stable
200Hg 23.1% stable
201Hg 13.2% stable
202Hg 29.7% stable
203Hg synth 46.61 d β 203Tl
204Hg 6.82% stable
 Category: Mercury (element)
| references

Mercury is a chemical element; it has symbol Hg and atomic number 80. It is commonly known as quicksilver. A heavy, silvery d-block element, mercury is the only metallic element that is known to be liquid at standard temperature and pressure;[a] the only other element that is liquid under these conditions is bromine, one of the halogens, though metals such as caesium, gallium, and rubidium melt just above room temperature.[b]

Mercury occurs in deposits throughout the world mostly as cinnabar (mercuric sulfide). The red pigment vermilion is obtained by grinding natural cinnabar or synthetic mercuric sulfide. Exposure to mercury and mercury-containing organic compounds is toxic to the nervous system, immune system and kidneys of humans and other animals; mercury poisoning can result from exposure to water-soluble forms of mercury (such as mercuric chloride or methylmercury) either directly or through mechanisms of biomagnification.

Mercury is used in thermometers, barometers, manometers, sphygmomanometers, float valves, mercury switches, mercury relays, fluorescent lamps and other devices, although concerns about the element's toxicity have led to the phasing out of—or reduction in the amount of mercury used in—these instruments.[11] It remains in use in scientific research applications and in amalgam for dental restoration in some locales. It is also still used in fluorescent lighting, although the quantity of mercury used is now smaller. Electricity passed through mercury vapor in a fluorescent lamp produces short-wave ultraviolet light, which then causes the phosphor in the tube to fluoresce, making visible light.

Properties

[edit]

Physical properties

[edit]
An old[12] pound coin (density ~7.6 g/cm3) floats on mercury due to the buoyancy force upon it and appears to float higher because of the strong surface tension of the mercury.

Mercury is a heavy, silvery-white metal that is liquid at room temperature. Compared to other metals, it is a poor conductor of heat, but a fair conductor of electricity.[13]

It has a melting point of −38.83 °C[c] and a boiling point of 356.73 °C,[d][14][15][16] both the lowest of any stable metal, although preliminary experiments on copernicium and flerovium have indicated that they have even lower boiling points.[17] This effect is due to lanthanide contraction and relativistic contraction reducing the orbit radius of the outermost electrons, and thus weakening the metallic bonding in mercury.[14] Upon freezing, the volume of mercury decreases by 3.59% and its density changes from 13.69 g/cm3 when liquid to 14.184 g/cm3 when solid. The coefficient of volume expansion is 181.59 × 10−6 at 0 °C, 181.71 × 10−6 at 20 °C and 182.50 × 10−6 at 100 °C (per °C). Solid mercury is malleable and ductile, and can be cut with a knife.[18]

Chemical properties

[edit]

Mercury does not react with most acids, such as dilute sulfuric acid, although oxidizing acids such as concentrated sulfuric acid and nitric acid or aqua regia dissolve it to give sulfate, nitrate, and chloride. Like silver, mercury reacts with atmospheric hydrogen sulfide. Mercury reacts with solid sulfur flakes, which are used in mercury spill kits to absorb mercury (spill kits also use activated carbon and powdered zinc).[19]

Amalgams

[edit]
Mercury-discharge spectral calibration lamp

Mercury dissolves many metals such as gold and silver to form amalgams. Iron is an exception, and iron flasks have traditionally been used to transport the material.[20] Several other first row transition metals (with the exception of manganese, copper and zinc) are also resistant in forming amalgams. Other elements that do not readily form amalgams with mercury include platinum.[21][22] Sodium amalgam is a common reducing agent in organic synthesis, and is also used in high-pressure sodium lamps.

Mercury readily combines with aluminium to form a mercury-aluminium amalgam when the two pure metals come into contact.[citation needed] Since the amalgam destroys the aluminium oxide layer which protects metallic aluminium from oxidizing in-depth (as in iron rusting), even small amounts of mercury can seriously corrode aluminium. For this reason, mercury is not allowed aboard an aircraft under most circumstances because of the risk of it forming an amalgam with exposed aluminium parts in the aircraft.[23]

Mercury embrittlement is the most common type of liquid metal embrittlement, as mercury is a natural component of some hydrocarbon reservoirs and will come into contact with petroleum processing equipment under normal conditions.[24]

Isotopes

[edit]

There are seven stable isotopes of mercury, with 202
Hg
being the most abundant (29.86%). The longest-lived radioisotopes are 194
Hg
with a half-life of 444 years, and 203
Hg
with a half-life of 46.612 days. Most of the remaining radioisotopes have half-lives that are less than a day. 206
Hg
occurs naturally in tiny traces as an intermediate decay product of 238
U
. 199
Hg
and 201
Hg
are the most often studied NMR-active nuclei, having spins of 12 and 32 respectively.[13]

Table of properties

[edit]
Table of thermal and physical properties of liquid mercury[25][26]
Temperature
(°C)
Density
(kg/m3)
Specific heat
(kJ/(kg·K))
Kinematic viscosity
(m2/s)
Conductivity
(W/(m·K))
Thermal diffusivity
(m2/s)
Prandtl number Bulk modulus
(K−1)
0 13628.22 0.1403 1.24 × 10−7 8.20 4.30 × 10−6 0.0288 0.000181
20 13579.04 0.1394 1.14 × 10−7 8.69 4.61 × 10−6 0.0249 0.000181
50 13505.84 0.1386 1.04 × 10−7 9.40 5.02 × 10−6 0.0207 0.000181
100 13384.58 0.1373 9.28 × 10−8 10.51 5.72 × 10−6 0.0162 0.000181
150 13264.28 0.1365 8.53 × 10−8 11.49 6.35 × 10−6 0.0134 0.000181
200 13144.94 0.1570 8.02 × 10−8 12.34 6.91 × 10−6 0.0116 0.000181
250 13025.60 0.1357 7.65 × 10−8 13.07 7.41 × 10−6 0.0103 0.000183
315.5 12847.00 0.1340 6.73 × 10−8 14.02 8.15 × 10−6 0.0083 0.000186

Etymology

[edit]
The symbol for the planet Mercury (☿) has been used since ancient times to represent the element

Hg is the modern chemical symbol for mercury.[27] It is an abbreviation of hydrargyrum, a romanized form of the ancient Greek name for mercury, ὑδράργυρος (hydrargyros). Hydrargyrum (/hˈdrɑːrərəm/ hy-DRAR-jər-əm)[28] has also been used in English, though the term is now dated. Hydrargyros is a Greek compound word meaning 'water-silver', from ὑδρ- (hydr-), the root of ὕδωρ (hydor) 'water', and ἄργυρος (argyros) 'silver'.[28] Like the English name quicksilver ('living-silver'), this name was due to mercury's liquid and shiny properties.[29]

The modern English name mercury comes from the planet Mercury. In medieval alchemy, the seven known metals—quicksilver, gold, silver, copper, iron, tin, and lead—were associated with the seven classical planets (Mercury, the sun, moon, Venus, Mars, Jupiter, and Saturn respectively). Quicksilver was associated with the fastest planet, which had been named after the Roman god Mercury, who was associated with speed and mobility. The astrological symbol for the planet became one of the alchemical symbols for the metal, and Mercury became an alternative name for the metal. Mercury is the only metal for which the alchemical planetary name survives, as it was decided it was preferable to quicksilver as a chemical name.[30][31]

History

[edit]

Mercury was found in Egyptian tombs that date from 1500 BC;[32] cinnabar, the most common natural source of mercury, has been in use since the Neolithic Age.[33]

In China and Tibet, mercury use was thought to prolong life, heal fractures, and maintain generally good health, although it is now known that exposure to mercury vapor leads to serious adverse health effects.[34] The first emperor of a unified China, Qín Shǐ Huáng Dì—allegedly buried in a tomb that contained rivers of flowing mercury on a model of the land he ruled, representative of the rivers of China—was reportedly killed by drinking a mercury and powdered jade mixture formulated by Qin alchemists intended as an elixir of immortality.[35][36] Khumarawayh ibn Ahmad ibn Tulun, the second Tulunid ruler of Egypt (r. 884–896), known for his extravagance and profligacy, reportedly built a basin filled with mercury, on which he would lie on top of air-filled cushions and be rocked to sleep.[37]

In November 2014 "large quantities" of mercury were discovered in a chamber 60 feet below the 1800-year-old pyramid known as the Temple of the Feathered Serpent, the third-largest pyramid of Teotihuacan, Mexico, along with "jade statues, jaguar remains, a box filled with carved shells and rubber balls".[38] In Lamanai, once a major city of the Maya civilization, a pool of mercury was found under a marker in a Mesoamerican ballcourt.[39][40]

Aristotle recounts that Daedalus made a wooden statue of Aphrodite move by pouring quicksilver in its interior.[41] In Greek mythology Daedalus gave the appearance of voice in his statues using quicksilver. The ancient Greeks used cinnabar (mercury sulfide) in ointments; the ancient Egyptians and the Romans used it in cosmetics. By 500 BC mercury was used to make amalgams (Medieval Latin amalgama, "alloy of mercury") with other metals.[42]

Alchemists thought of mercury as the First Matter from which all metals were formed. They believed that different metals could be produced by varying the quality and quantity of sulfur contained within the mercury. The purest of these was gold, and mercury was called for in attempts at the transmutation of base (or impure) metals into gold, which was the goal of many alchemists.[30]

The mines in Almadén (Spain), Monte Amiata (Italy), and Idrija (now Slovenia) dominated mercury production from the opening of the mine in Almadén 2500 years ago, until new deposits were found at the end of the 19th century.[43]

The location of major 18th century Spanish silver mine districs (crossed pickaxes) and the mines involved in mercury supply needed for silver mining (purple dots).

Beginning in 1558, with the invention of the patio process to extract silver from ore using mercury, mercury became an essential resource in the economy of Spain and its American colonies. Mercury was used to extract silver from the lucrative mines in New Spain and Peru. Initially, the Spanish Crown's mines in Almadén in Southern Spain supplied all the mercury for the colonies.[44] Mercury deposits were discovered in the New World, and more than 100,000 tons of mercury were mined from the region of Huancavelica, Peru, over the course of three centuries following the discovery of deposits there in 1563.[45] In 1786 the main mine at Huancavelica suffered a sudden collapse that killed over 100 persons and greatly reduced the mine's output.[46] Through the legalization of scavenging known as pallaqueo mercury production rose again peaking in 1794–1796.[47] The French Revolutionary Wars disrupted European mercury supply to Spanish America leading to an increasing reliance for the mines in present-day Peru and Bolivia on mercury from Huancavelica but this mines production was clearly by 1799 not enough to supply the demand in the Andean mines.[47] Spain abolished the royal mercury monopoly in 1813.[47]

Mercury poisoning in the mines left many people disabled through the early modern period but mercury itself was not the chief cause of deaths in the mines.[48]

The patio process and later pan amalgamation process continued to create great demand for mercury to treat silver ores until the late 19th century.[45]

Occurrence

[edit]

Mercury is an extremely rare element in Earth's crust; it has an average crustal abundance by mass of only 0.08 parts per million (ppm)[49] and is the 66th most abundant element in the Earth's crust.[50] Because it does not blend geochemically with those elements that constitute the majority of the crustal mass, mercury ores can be extraordinarily concentrated considering the element's abundance in ordinary rock. The richest mercury ores contain up to 2.5% mercury by mass, and even the leanest concentrated deposits are at least 0.1% mercury (12,000 times average crustal abundance). It is found either as a native metal (rare) or in cinnabar, metacinnabar, sphalerite, corderoite, livingstonite and other minerals, with cinnabar (HgS) being the most common ore.[51][52] Mercury ores often occur in hot springs or other volcanic regions.[53]

Native mercury with cinnabar, Socrates mine, Sonoma County, California. Cinnabar sometimes alters to native mercury in the oxidized zone of mercury deposits.

Former mines in Italy, the United States and Mexico, which once produced a large proportion of the world supply, have now been completely mined out or, in the case of Slovenia (Idrija) and Spain (Almadén), shut down due to the fall of the price of mercury. Nevada's McDermitt Mine, the last mercury mine in the United States, closed in 1992. The price of mercury has been highly volatile over the years and in 2006 was $650 per 76-pound (34.46 kg) flask.[54]

Mercury is extracted by heating cinnabar in a current of air and condensing the vapor. The equation for this extraction is:

HgS + O2 → Hg + SO2
Evolution of mercury price (U.S.) and production (worldwide)

In 2020, China was the top producer of mercury, providing 88% of the world output (2200 out of 2500 tonnes), followed by Tajikistan (178 t), Russia (50 t) and Mexico (32 t).[55]

Mercury production by country in 2022–24 (tonnes)[56][57]
Country Production
World 1,200
 China * 1,000
 Tajikistan * 100
 Peru * 30
Russia 30
 Norway * 20
United States 15
Mexico 10
 Kyrgyzstan 6
Morocco 2

Because of the high toxicity of mercury, both the mining of cinnabar and refining for mercury are hazardous and historic causes of mercury poisoning.[58] In China, prison labor was used by a private mining company as recently as the 1950s to develop new cinnabar mines. Thousands of prisoners were used by the Luo Xi mining company to establish new tunnels.[59] Worker health in functioning mines is at high risk.

A newspaper claimed that an unidentified European Union directive calling for energy-efficient lightbulbs to be made mandatory by 2012 encouraged China to re-open cinnabar mines to obtain the mercury required for CFL bulb manufacture. Environmental dangers have been a concern, particularly in the southern cities of Foshan and Guangzhou, and in Guizhou province in the southwest.[59]

Abandoned mercury mine processing sites often contain very hazardous waste piles of roasted cinnabar calcines. Water run-off from such sites is a recognized source of ecological damage. Former mercury mines may be suited for constructive re-use; for example, in 1976 Santa Clara County, California purchased the historic Almaden Quicksilver Mine and created a county park on the site, after conducting extensive safety and environmental analysis of the property.[60][61]

Chemistry

[edit]

All known mercury compounds exhibit one of two positive oxidation states: I and II. Experiments have failed to unequivocally demonstrate any higher oxidation states: both the claimed 1976 electrosynthesis of an unstable Hg(III) species and 2007 cryogenic isolation of HgF4 have disputed interpretations and remain difficult (if not impossible) to reproduce.[62]

Compounds of mercury(I)

[edit]

Unlike its lighter neighbors, cadmium and zinc, mercury usually forms simple stable compounds with metal-metal bonds. Most mercury(I) compounds are diamagnetic and feature the dimeric cation, Hg2+
2
. Stable derivatives include the chloride and nitrate. In aqueous solution of a mercury(I) salt, slight disproportion of Hg2+
2
into Hg and Hg2+
results in >0.5% of dissolved mercury existing as Hg2+
. In these solutions, complexation of the Hg2+
with addition of ligands such as cyanide causes disproportionation to go to completion, with all Hg2+
2
precipitating as elemental mercury and insoluble mercury(II) compounds (e.g. mercury(II) cyanide if cyanide is used as the ligand).[63] Mercury(I) chloride, a colorless solid also known as calomel, is really the compound with the formula Hg2Cl2, with the connectivity Cl-Hg-Hg-Cl. It reacts with chlorine to give mercury(II) chloride, which resists further oxidation. Mercury(I) hydride, a colorless gas, has the formula HgH, containing no Hg-Hg bond; however, the gas has only ever been observed as isolated molecules.[64]

Indicative of its tendency to bond to itself, mercury forms mercury polycations, which consist of linear chains of mercury centers, capped with a positive charge. One example is Hg
3
(AsF
6
)

2
containing the Hg2+
3
cation.[65]

Compounds of mercury(II)

[edit]

Mercury(II) is the most common oxidation state and is the main one in nature as well. All four mercuric halides are known and have been demonstrated to form linear coordination geometry, despite mercury's tendency to form tetrahedral molecular geometry with other ligands. This behavior is similar to the Ag+ ion. The best known mercury halide is mercury(II) chloride, an easily sublimating white solid.[66]

Mercury(II) oxide, the main oxide of mercury, arises when the metal is exposed to air for long periods at elevated temperatures. It reverts to the elements upon heating near 400 °C, as was demonstrated by Joseph Priestley in an early synthesis of pure oxygen.[19] Hydroxides of mercury are poorly characterized, as attempted isolation studies of mercury(II) hydroxide have yielded mercury oxide instead.[67]

Being a soft metal, mercury forms very stable derivatives with the heavier chalcogens. Preeminent is mercury(II) sulfide, HgS, which occurs in nature as the ore cinnabar and is the brilliant pigment vermilion. Like ZnS, HgS crystallizes in two forms, the reddish cubic form and the black zinc blende form.[13] The latter sometimes occurs naturally as metacinnabar.[52] Mercury(II) selenide (HgSe) and mercury(II) telluride (HgTe) are known, these as well as various derivatives, e.g. mercury cadmium telluride and mercury zinc telluride being semiconductors useful as infrared detector materials.[68]

Mercury(II) salts form a variety of complex derivatives with ammonia. These include Millon's base (Hg2N+), the one-dimensional polymer (salts of HgNH+
2
)
n
), and "fusible white precipitate" or [Hg(NH3)2]Cl2. Known as Nessler's reagent, potassium tetraiodomercurate(II) (K
2
HgI
4
) is still occasionally used to test for ammonia owing to its tendency to form the deeply colored iodide salt of Millon's base.[69]

Mercury fulminate is a detonator widely used in explosives.[13]

Organomercury compounds

[edit]

Organic mercury compounds are historically important but are of little industrial value in the western world. Mercury(II) salts are a rare example of simple metal complexes that react directly with aromatic rings. Organomercury compounds are always divalent and usually two-coordinate and linear geometry. Unlike organocadmium and organozinc compounds, organomercury compounds do not react with water. They usually have the formula HgR2, which are often volatile, or HgRX, which are often solids, where R is aryl or alkyl and X is usually halide or acetate. Methylmercury, a generic term for compounds with the formula CH3HgX, is a dangerous family of compounds that are often found in polluted water.[70] They arise by a process known as biomethylation.

Applications

[edit]
The bulb of a mercury-in-glass thermometer

Mercury is used primarily for the manufacture of industrial chemicals or for electrical and electronic applications. It is used in some liquid-in-glass thermometers, especially those used to measure high temperatures. A still increasing amount is used as gaseous mercury in fluorescent lamps, while most of the other applications are slowly being phased out due to health and safety regulations. In some applications, mercury is replaced with less toxic but considerably more expensive Galinstan alloy.[71]

Medicine

[edit]
Amalgam filling

Historical and folk

[edit]

Mercury and its compounds have been used in medicine, although they are much less common today than they once were, now that the toxic effects of mercury and its compounds are more widely understood. An example of the early therapeutic application of mercury was published in 1787 by James Lind.[72]

The first edition of The Merck Manuals (1899) featured many then-medically relevant mercuric compounds, such as mercury-ammonium chloride, yellow mercury proto-iodide, calomel, and mercuric chloride, among others.[73]

Mercury in the form of one of its common ores, cinnabar, is used in various traditional medicines, especially in traditional Chinese medicine. Review of its safety has found that cinnabar can lead to significant mercury intoxication when heated, consumed in overdose, or taken long term, and can have adverse effects at therapeutic doses, though effects from therapeutic doses are typically reversible. Although this form of mercury appears to be less toxic than other forms, its use in traditional Chinese medicine has not yet been justified, as the therapeutic basis for the use of cinnabar is not clear.[74]

Mercury(I) chloride (also known as calomel or mercurous chloride) has been used in traditional medicine as a diuretic, topical disinfectant, and laxative. Mercury(II) chloride (also known as mercuric chloride or corrosive sublimate) was once used to treat syphilis (along with other mercury compounds), although it is so toxic that sometimes the symptoms of its toxicity were confused with those of the syphilis it was believed to treat.[75] It is also used as a disinfectant. Blue mass, a pill or syrup in which mercury is the main ingredient, was prescribed throughout the 19th century for numerous conditions including constipation, depression, child-bearing and toothaches.[76] In the early 20th century, mercury was administered to children yearly as a laxative and dewormer, and it was used in teething powders for infants. The mercury-containing organohalide merbromin (sometimes sold as Mercurochrome) is still widely used but has been banned in some countries, such as the U.S.[77]

Contemporary

[edit]

Mercury is an ingredient in dental amalgams.[78]

Thiomersal (called Thimerosal in the United States) is an organic compound used as a preservative in vaccines, although this use is in decline.[79] Although it was widely speculated that this mercury-based preservative could cause or trigger autism in children, no evidence supports any such link.[80] Nevertheless, thiomersal has been removed from, or reduced to trace amounts in, all U.S. vaccines recommended for children 6 years of age and under, with the exception of the inactivated influenza vaccine.[79] Merbromin (Mercurochrome), another mercury compound, is a topical antiseptic used for minor cuts and scrapes in some countries. Today, the use of mercury in medicine has greatly declined in all respects, especially in developed countries.[81]

Mercury is still used in some diuretics, although substitutes such as thiazides now exist for most therapeutic uses.[82] In 2003, mercury compounds were found in some over-the-counter drugs, including topical antiseptics, stimulant laxatives, diaper-rash ointment, eye drops, and nasal sprays. The FDA has "inadequate data to establish general recognition of the safety and effectiveness" of the mercury ingredients in these products.[83]

Production of chlorine and caustic soda

[edit]

Chlorine is produced from sodium chloride (common salt, NaCl) using electrolysis to separate metallic sodium from chlorine gas. Usually salt is dissolved in water to produce a brine. By-products of any such chloralkali process are hydrogen (H2) and sodium hydroxide (NaOH), which is commonly called caustic soda or lye. By far the largest use of mercury[84][85] in the late 20th century was in the mercury cell process (also called the Castner-Kellner process) where metallic sodium is formed as an amalgam at a cathode made from mercury; this sodium is then reacted with water to produce sodium hydroxide.[86] Many of the industrial mercury releases of the 20th century came from this process, although modern plants claim to be safe in this regard.[85] From the 1960s onward, the majority of industrial plants moved away from mercury cell processes towards diaphragm cell technologies to produce chlorine, though 11% of the chlorine made in the United States was still produced with the mercury cell method as of 2005.[87]

Laboratory uses

[edit]

Thermometers

[edit]

Thermometers containing mercury were invented in the early 18th century by Daniel Gabriel Fahrenheit, though earlier attempts at making temperature-measuring instruments filled with quicksilver had been described in the 1650s.[88]: 23  Fahrenheit's mercury thermometer was based on an earlier design that used alcohol rather than mercury; the mercury thermometer was significantly more accurate than those using alcohol.[89] From the early 21st century onwards, the use of mercury thermometers has been declining, and mercury-containing instruments have been banned in many jurisdictions following the 1998 Protocol on Heavy Metals.[90][91] Modern alternatives to mercury thermometers include resistance thermometers, thermocouples, and thermistor sensors that output to a digital display.[92]

Mirrors

[edit]

Some transit telescopes use a basin of mercury to form a flat and absolutely horizontal mirror, useful in determining an absolute vertical or perpendicular reference. Concave horizontal parabolic mirrors may be formed by rotating liquid mercury on a disk, the parabolic form of the liquid thus formed reflecting and focusing incident light. Such liquid-mirror telescopes are cheaper than conventional large mirror telescopes by up to a factor of 100, but the mirror cannot be tilted and always points straight up.[93][94][95]

Electrochemistry

[edit]

Liquid mercury is part of a popular secondary reference electrode (called the calomel electrode) in electrochemistry as an alternative to the standard hydrogen electrode. The calomel electrode is used to work out the electrode potential of half cells.[96] The triple point of mercury, −38.8344 °C, is a fixed point used as a temperature standard for the International Temperature Scale (ITS-90).[13]

Polarography and crystallography

[edit]

In polarography, both the dropping mercury electrode[97] and the hanging mercury drop electrode[98] use elemental mercury. This use allows a new uncontaminated electrode to be available for each measurement or each new experiment.

Mercury-containing compounds are also of use in the field of structural biology. Mercuric compounds such as mercury(II) chloride or potassium tetraiodomercurate(II) can be added to protein crystals in an effort to create heavy atom derivatives that can be used to solve the phase problem in X-ray crystallography via isomorphous replacement or anomalous scattering methods.[99]

Niche uses

[edit]

Gaseous mercury is used in mercury-vapor lamps, fluorescent lamps, and some neon signs. Those low-pressure lamps emit very spectrally narrow lines, which are traditionally used in optical spectroscopy for calibration of spectral position. Commercial calibration lamps are sold for this purpose; reflecting a fluorescent ceiling light into a spectrometer is a common calibration practice.[100] Gaseous mercury is also found in some electron tubes, including ignitrons, thyratrons, and mercury arc rectifiers.[101] It is also used in specialist medical care lamps for skin tanning and disinfection.[102] Gaseous mercury is added to cold cathode argon-filled lamps to increase the ionization and electrical conductivity. An argon-filled lamp without mercury will have dull spots and will fail to light correctly. Lighting containing mercury can be bombarded/oven pumped only once. When added to neon filled tubes, inconsistent red and blue spots are produced in the light emissions until the initial burning-in process is completed; eventually it will light a consistent dull off-blue color.[103]

The Deep Space Atomic Clock (DSAC) under development by the Jet Propulsion Laboratory utilises mercury in a linear ion-trap-based clock. The novel use of mercury permits the creation of compact atomic clocks with low energy requirements ideal for space probes and Mars missions.[104]

Skin whitening

[edit]

Mercury is effective as an active ingredient in skin whitening compounds used to depigment skin.[105] The Minamata Convention on Mercury limits the concentration of mercury in such whiteners to 1 part per million. However, as of 2022, many commercially sold whitener products continue to exceed that limit, and are considered toxic.[106]

Firearms

[edit]

Mercury(II) fulminate is a primary explosive, which has mainly been used as a primer of a cartridge in firearms throughout the 19th and 20th centuries.[107]

Mining

[edit]

Mercury is used in illegal gold mining to help separate gold particles from a mixture of sand or gravel and water.[108] Small gold particles may form mercury-gold amalgam and therefore increase the gold recovery rates.[13] The use of mercury causes a severe pollution problem in places such as Ghana.[108]

Historic uses

[edit]
A single-pole, single-throw (SPST) mercury switch
Mercury manometer to measure pressure

Many historic applications made use of the peculiar physical properties of mercury, especially as a dense liquid and a liquid metal:

  • Quantities of liquid mercury ranging from 90 to 600 grams (3.2 to 21.2 oz) have been recovered from elite Maya tombs (100–700 AD)[38] or ritual caches at six sites. This mercury may have been used in bowls as mirrors for divinatory purposes. Five of these date to the Classic Period of Maya civilization (c. 250–900) but one example predated this.[109]
  • In Islamic Spain, it was used for filling decorative pools. Later, the American artist Alexander Calder built a mercury fountain for the Spanish Pavilion at the 1937 World Exhibition in Paris. The fountain is now on display at the Fundació Joan Miró in Barcelona.[110]
  • The Fresnel lenses of old lighthouses used to float and rotate in a bath of mercury which acted like a bearing.[111]
  • Mercury sphygmomanometers, barometers, diffusion pumps, coulometers, and many other laboratory instruments took advantage of mercury's properties as a very dense, opaque liquid with a nearly linear thermal expansion.[112]
  • As an electrically conductive liquid, it was used in mercury switches (including home mercury light switches installed prior to 1970), tilt switches used in old fire detectors and in some home thermostats.[113]
  • Owing to its acoustic properties, mercury was used as the propagation medium in delay-line memory devices used in early digital computers of the mid-20th century, such as the SEAC computer.[114]
  • In 1911, Heike Kamerlingh Onnes discovered superconductivity through the cooling of mercury below 4 kelvin shortly after the discovery and production of liquid helium.[115] Its superconductive properties were later determined to be unusual compared to other later-discovered superconductors, such as the more popular niobium alloys.[116][117]
  • Experimental mercury vapor turbines were installed to increase the efficiency of fossil-fuel electrical power plants.[118] The South Meadow power plant in Hartford, CT employed mercury as its working fluid, in a binary configuration with a secondary water circuit, for a number of years starting in the late 1920s in a drive to improve plant efficiency. Several other plants were built, including the Schiller Station in Portsmouth, NH, which went online in 1950. The idea did not catch on industry-wide due to the weight and toxicity of mercury, as well as the advent of supercritical steam plants in later years.[119][120]
  • Similarly, liquid mercury was used as a coolant for some nuclear reactors; however, sodium is proposed for reactors cooled with liquid metal, because the high density of mercury requires much more energy to circulate as coolant.[121]
  • Mercury was a propellant for early ion engines in electric space propulsion systems. Advantages were mercury's high molecular weight, low ionization energy, low dual-ionization energy, high liquid density and liquid storability at room temperature. Disadvantages were concerns regarding environmental impact associated with ground testing and concerns about eventual cooling and condensation of some of the propellant on the spacecraft in long-duration operations. The first spaceflight to use electric propulsion was a mercury-fueled ion thruster developed at NASA Glenn Research Center and flown on the Space Electric Rocket Test "SERT-1" spacecraft launched by NASA at its Wallops Flight Facility in 1964. The SERT-1 flight was followed up by the SERT-2 flight in 1970. Mercury and caesium were preferred propellants for ion engines until Hughes Research Laboratory performed studies finding xenon gas to be a suitable replacement. Xenon is now the preferred propellant for ion engines, as it has a high molecular weight, little or no reactivity due to its noble gas nature, and high liquid density under mild cryogenic storage.[122][123]

Other applications made use of the chemical properties of mercury:

  • The mercury battery is a non-rechargeable electrochemical battery, a primary cell, that was common in the middle of the 20th century. It was used in a wide variety of applications and was available in various sizes, particularly button sizes. Its constant voltage output and long shelf life gave it a niche use for camera light meters and hearing aids. The mercury cell was effectively banned in most countries in the 1990s due to concerns about the mercury contaminating landfills.[124]
  • Mercury was used for preserving wood, developing daguerreotypes, silvering mirrors,[125] anti-fouling paints,[126] herbicides,[127] interior latex paint, handheld maze games, cleaning, and road leveling devices in cars. Mercury compounds have been used in antiseptics, laxatives, antidepressants, and in antisyphilitics.[76] Mercury has been replaced with safer compounds in most, if not all, of these applications.
  • It was allegedly used by allied spies to sabotage Luftwaffe planes: a mercury paste was applied to bare aluminium, causing the metal to rapidly corrode; this would cause structural failures.[128]
  • Mercury was once used as a gun barrel bore cleaner.[129][130]
  • From the mid-18th to the mid-19th centuries, a process called "carroting" was used in the making of felt hats. Animal skins were rinsed in an orange solution (the term "carroting" arose from this color) of the mercury compound mercuric nitrate, Hg(NO3)2.[131] This process separated the fur from the pelt and matted it together. This solution and the vapors it produced were highly toxic. The United States Public Health Service banned the use of mercury in the felt industry in December 1941. The psychological symptoms associated with mercury poisoning inspired the phrase "mad as a hatter".[132] Lewis Carroll's "Mad Hatter" in his book Alice's Adventures in Wonderland was a play on words based on the older phrase, but the character himself does not exhibit symptoms of mercury poisoning.[133]
  • Historically, mercury was used extensively in hydraulic gold mining (see #Mining. Large-scale use of mercury stopped in the 1960s. However, mercury is still used in small scale, often clandestine, gold prospecting. It is estimated that 45,000 metric tons of mercury used in California for placer mining have not been recovered.[134] Mercury was also used in silver mining to extract the metal from ore through the patio process.[135]

Toxicity and safety

[edit]
Mercury
Hazards
GHS labelling:
GHS06: ToxicGHS08: Health hazardGHS09: Environmental hazard
Danger
H330, H360D, H372, H410
P201, P233, P260, P273, P280, P304, P308, P310, P313, P340, P391, P403[136]
NFPA 704 (fire diamond)
NFPA 704 four-colored diamondHealth 2: Intense or continued but not chronic exposure could cause temporary incapacitation or possible residual injury. E.g. chloroformFlammability 0: Will not burn. E.g. waterInstability 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazards (white): no code
2
0
0

Due to its physical properties and relative chemical inertness, liquid mercury is absorbed very poorly through intact skin and the gastrointestinal tract.[137] Mercury vapor is the primary hazard of elemental mercury. As a result, containers of mercury are securely sealed to avoid spills and evaporation. Heating of mercury, or of compounds of mercury that may decompose when heated, should be carried out with adequate ventilation in order to minimize exposure to mercury vapor. The most toxic forms of mercury are its organic compounds, such as dimethylmercury and methylmercury. Mercury can cause both chronic and acute poisoning.[138][139]

Releases in the environment

[edit]
Amount of atmospheric mercury deposited at Wyoming's Upper Fremont Glacier over the last 270 years

Preindustrial deposition rates of mercury from the atmosphere may be about 4 ng per 1 L of ice deposited. Volcanic eruptions and related natural sources are responsible for approximately half of atmospheric mercury emissions.[140]

Atmospheric mercury contamination in outdoor urban air at the start of the 21st century was measured at 0.01–0.02 μg/m3. A 2001 study measured mercury levels in 12 indoor sites chosen to represent a cross-section of building types, locations and ages in the New York area. This study found mercury concentrations significantly elevated over outdoor concentrations, at a range of 0.0065 – 0.523 μg/m3. The average was 0.069 μg/m3.[141]

Half of mercury emissions are attributed to mankind. The sources can be divided into the following estimated percentages:[142]

  • 65% from stationary combustion, of which coal-fired power plants are the largest aggregate source (40% of U.S. mercury emissions in 1999). This includes power plants fueled with gas where the mercury has not been removed. Emissions from coal combustion are between one and two orders of magnitude higher than emissions from oil combustion, depending on the country.[142]
  • 11% from gold production. The three largest point sources for mercury emissions in the U.S. are the three largest gold mines. Hydrogeochemical release of mercury from gold-mine tailings has been accounted as a significant source of atmospheric mercury in eastern Canada.[143]
  • 6.8% from non-ferrous metal production, typically smelters.
  • 6.4% from cement production.
  • 3.0% from waste disposal, including municipal and hazardous waste, crematoria, and sewage sludge incineration.
  • 3.0% from caustic soda production.
  • 1.4% from pig iron and steel production.
  • 1.1% from mercury production, mainly for batteries.
  • 2.0% from other sources.

The above percentages are estimates of the global human-caused mercury emissions in 2000, excluding biomass burning, an important source in some regions.[142]

A serious industrial disaster was the dumping of waste mercury compounds into Minamata Bay, Japan, between 1932 and 1968. It is estimated that over 3,000 people suffered various deformities, severe mercury poisoning symptoms or death from what became known as Minamata disease.[144][145]

China is estimated to produce 50% of mercury emissions, most of which result from production of vinyl chloride.[146]

Joss paper burning on the street, a common tradition practiced in Asia, Hong Kong, 2023

Mercury also enters into the environment through the improper disposal of mercury-containing products.[147] Due to health concerns, toxics use reduction efforts are cutting back or eliminating mercury in such products. For example, the amount of mercury sold in thermostats in the United States decreased from 14.5 tons in 2004 to 3.9 tons in 2007.[148]

The tobacco plant readily absorbs and accumulates heavy metals such as mercury from the surrounding soil into its leaves. These are subsequently inhaled during tobacco smoking.[149] While mercury is a constituent of tobacco smoke,[150] studies have largely failed to discover a significant correlation between smoking and mercury uptake by humans compared to sources such as occupational exposure, fish consumption, and amalgam tooth fillings.[151]

A less well-known source of mercury is the burning of joss paper,[152] which is a common tradition practiced in Asia, including China,[153] Vietnam, Hong Kong, Thailand, Taiwan and Malaysia.[154]

Spill cleanup

[edit]

Mercury spills pose an immediate threat to people handling the material, in addition to being an environmental hazard if the material is not contained properly. This is of particular concern for visible mercury, or mercury in liquid state, as its unusual appearance and behavior for a metal makes it an attractive nuisance to the uninformed.[155] Procedures have been developed to contain mercury spills, as well as recommendations on appropriate responses based on the conditions of a spill.[156][157] Tracking liquid mercury away from the site of a spill is a major concern in liquid mercury spills; regulations emphasize containment of the visible mercury as the first course of action, followed by monitoring of mercury vapors and vapor cleanup. Several products are sold as mercury spill adsorbents, ranging from metal salts to polymers and zeolites.[158]

Sediment contamination

[edit]

Sediments within large urban-industrial estuaries act as an important sink for point source and diffuse mercury pollution within catchments.[159] A 2015 study of foreshore sediments from the Thames estuary measured total mercury at 0.01 to 12.07 mg/kg with mean of 2.10 mg/kg and median of 0.85 mg/kg (n = 351).[159] The highest mercury concentrations were shown to occur in and around the city of London in association with fine grain muds and high total organic carbon content.[159] The strong affinity of mercury for carbon rich sediments has also been observed in salt marsh sediments of the River Mersey, with a mean concentration of 2 mg/kg, up to 5 mg/kg.[160] These concentrations are far higher than those in the salt marsh river creek sediments of New Jersey and mangroves of Southern China, which exhibit low mercury concentrations of about 0.2 mg/kg.[161][162]

Occupational exposure

[edit]
EPA workers clean up residential mercury spill in 2004

Due to the health effects of mercury exposure, industrial and commercial uses are regulated in many countries. The World Health Organization,[163] OSHA, and NIOSH all treat mercury as an occupational hazard; both OSHA and NIOSH, among other regulatory agencies, have established specific occupational exposure limits on the element and its derivative compounds in liquid and vapor form.[164][165] Environmental releases and disposal of mercury are regulated in the U.S. primarily by the United States Environmental Protection Agency.

Fish

[edit]

Fish and shellfish have a natural tendency to concentrate mercury in their bodies, often in the form of methylmercury, a highly toxic organic compound of mercury. Species of fish that are high on the food chain, such as shark, swordfish, king mackerel, bluefin tuna, albacore tuna, and tilefish contain higher concentrations of mercury than others. Because mercury and methylmercury are fat soluble, they primarily accumulate in the viscera, although they are also found throughout the muscle tissue.[166] Mercury presence in fish muscles can be studied using non-lethal muscle biopsies.[167] Mercury present in prey fish accumulates in the predator that consumes them. Since fish are less efficient at depurating than accumulating methylmercury, methylmercury concentrations in the fish tissue increase over time. Thus species that are high on the food chain amass body burdens of mercury that can be ten times higher than the species they consume. This process is called biomagnification. Mercury poisoning happened this way in Minamata, Japan, now called Minamata disease.[144][145]

In the Lower Amazon, mercury contamination in fish is driven by anthropogenic activities such as gold mining and deforestation, which release mercury into aquatic ecosystems.[168][169] Studies report mercury concentrations in fish muscle tissue ranging from 0.01 to 0.67 μg/g, with carnivorous species like Plagioscion squamosissimus showing higher levels due to biomagnification, sometimes exceeding the World Health Organization's safety threshold of 0.5 μg/g.[168] Local communities relying on fish as a dietary staple face potential health risks from mercury exposure. Mercury levels in aquatic species, including fish and shrimp (Macrobrachium amazonicum), indicate broader environmental contamination, particularly near mining areas.[170]

Cosmetics

[edit]

Some facial creams contain dangerous levels of mercury. Most contain comparatively non-toxic inorganic mercury, but products containing highly toxic organic mercury have been encountered.[171][172] New York City residents have been found to be exposed to significant levels of inorganic mercury compounds through the use of skin care products.[173]

Effects and symptoms of mercury poisoning

[edit]

Toxic effects include damage to the brain, kidneys and lungs. Mercury poisoning can result in several diseases, including acrodynia (pink disease), Hunter-Russell syndrome, and Minamata disease. Symptoms typically include sensory impairment (vision, hearing, speech), disturbed sensation and a lack of coordination. The type and degree of symptoms exhibited depend upon the individual toxin, the dose, and the method and duration of exposure. Case–control studies have shown effects such as tremors, impaired cognitive skills, and sleep disturbance in workers with chronic exposure to mercury vapor even at low concentrations in the range 0.7–42 μg/m3.[174][175]

A study has shown that acute exposure (4–8 hours) to calculated elemental mercury levels of 1.1 to 44 mg/m3 resulted in chest pain, dyspnea, cough, hemoptysis, impairment of pulmonary function, and evidence of interstitial pneumonitis.[138] Acute exposure to mercury vapor has been shown to result in profound central nervous system effects, including psychotic reactions characterized by delirium, hallucinations, and suicidal tendency. Occupational exposure has resulted in broad-ranging functional disturbance, including erethism, irritability, excitability, excessive shyness, and insomnia. With continuing exposure, a fine tremor develops and may escalate to violent muscular spasms. Tremor initially involves the hands and later spreads to the eyelids, lips, and tongue. Long-term, low-level exposure has been associated with more subtle symptoms of erethism, including fatigue, irritability, loss of memory, vivid dreams and depression.[139][176]

Treatment

[edit]

Research on the treatment of mercury poisoning is limited. Currently available drugs for acute mercurial poisoning include chelators N-acetyl-D,L-penicillamine (NAP), British Anti-Lewisite (BAL), 2,3-dimercapto-1-propanesulfonic acid (DMPS), and dimercaptosuccinic acid (DMSA). In one small study including 11 construction workers exposed to elemental mercury, patients were treated with DMSA and NAP.[177] Chelation therapy with both drugs resulted in the mobilization of a small fraction of the total estimated body mercury. DMSA was able to increase the excretion of mercury to a greater extent than NAP.[177]

Regulations

[edit]

International

[edit]

140 countries agreed in the Minamata Convention on Mercury by the United Nations Environment Programme (UNEP) to prevent mercury vapor emissions.[178] The convention was signed on 10 October 2013.[179]

United States

[edit]

In the United States, the Environmental Protection Agency is charged with regulating and managing mercury contamination. Several laws give the EPA this authority, including the Clean Air Act, the Clean Water Act, the Resource Conservation and Recovery Act, and the Safe Drinking Water Act. Additionally, the Mercury-Containing and Rechargeable Battery Management Act, passed in 1996, phases out the use of mercury in batteries, and provides for the efficient and cost-effective disposal of many types of used batteries.[180] North America contributed approximately 11% of the total global anthropogenic mercury emissions in 1995.[181]

The United States Clean Air Act, passed in 1990, put mercury on a list of toxic pollutants that need to be controlled to the greatest possible extent. Thus, industries that release high concentrations of mercury into the environment agreed to install maximum achievable control technologies (MACT). In March 2005, the EPA promulgated a regulation[182] that added power plants to the list of sources that should be controlled and instituted a national cap and trade system. States were given until November 2006 to impose stricter controls, but after a legal challenge from several states, the regulations were struck down by a federal appeals court on 8 February 2008. The rule was deemed not sufficient to protect the health of persons living near coal-fired power plants, given the negative effects documented in the EPA Study Report to Congress of 1998.[183] However newer data published in 2015 showed that after introduction of the stricter controls mercury declined sharply, indicating that the Clean Air Act had its intended impact.[184]

The EPA announced new rules for coal-fired power plants on 22 December 2011.[185] Cement kilns that burn hazardous waste are held to a looser standard than are standard hazardous waste incinerators in the United States, and as a result are a disproportionate source of mercury pollution.[186]

European Union

[edit]

In the European Union, the directive on the Restriction of the Use of Certain Hazardous Substances in Electrical and Electronic Equipment (see RoHS) bans mercury from certain electrical and electronic products, and limits the amount of mercury in other products to less than 1000 ppm.[187] There are restrictions for mercury concentration in packaging (the limit is 100 ppm for sum of mercury, lead, hexavalent chromium and cadmium) and batteries (the limit is 5 ppm).[188] In July 2007, the European Union also banned mercury in non-electrical measuring devices, such as thermometers and barometers. The ban applies to new devices only, and contains exemptions for the health care sector and a two-year grace period for manufacturers of barometers.[189]

Scandinavia

[edit]

Norway enacted a total ban on the use of mercury in the manufacturing and import/export of mercury products, effective 1 January 2008.[190] In 2002, several lakes in Norway were found to have a poor state of mercury pollution, with an excess of 1 μg/g of mercury in their sediment.[191] In 2008, Norway's Minister of Environment Development Erik Solheim said: "Mercury is among the most dangerous environmental toxins. Satisfactory alternatives to Hg in products are available, and it is therefore fitting to induce a ban."[192] Products containing mercury were banned in Sweden in 2009,[193][194] while elemental mercury has been banned from manufacture and use in all but a few applications (such as certain energy-saving light sources and amalgam dental fillings) in Denmark since 2008.[195]

See also

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Notes

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References

[edit]

Further reading

[edit]
[edit]
Revisions and contributorsEdit on WikipediaRead on Wikipedia
from Grokipedia
is a with the symbol Hg and 80, recognized as the only metallic element that remains at standard and pressure. Appearing as a dense, silvery-white substance with a of 13.55 g/cm³, it exhibits high and low , enabling it to form coherent droplets and flow readily. Its is -38.87°C and 356.73°C, properties that historically facilitated its use in scientific instruments despite its inherent . The element derives its name from the Roman god Mercury, reflecting its swift mobility, while the symbol Hg originates from the Latin hydrargyrum, meaning "watery silver," alluding to its fluid, metallic luster. Known to ancient civilizations including the and Chinese since approximately 1500 BCE, mercury occurs naturally primarily as the and has been extracted for millennia, often leading to widespread environmental contamination from mining residues. Its vapors and compounds pose severe health risks, causing neurological damage, , and developmental disorders through , , or absorption, with elemental mercury's volatility exacerbating indoor exposure hazards. Historically employed in thermometers, barometers, electrical switches, and dental amalgams due to its and amalgamating properties, mercury's applications have sharply declined following recognition of its bioaccumulative and global regulatory efforts, such as the Minamata Convention, which aims to phase out non-essential uses. Industrial production once centered on electrolytic methods from , but output has plummeted as alternatives like digital sensors replace mercury-containing devices, underscoring the tension between its unique physical attributes and causal health and ecological perils. Controversies persist over legacy pollution from sites like in and historical , where inadequate controls amplified human exposure and ecosystem disruption.

Properties

Physical properties

Mercury exists as a silvery-white liquid at , unique among metallic elements, with a of −38.87 °C and a of 356.73 °C. Its high of 13.534 g/cm³ at 25 °C contributes to its ability to support objects denser than but less dense than itself, such as a British pound . The element exhibits high of 470 dynes/cm at 20 °C, leading to the formation of coherent droplets and beads rather than spreading. Vapor is 0.002 mmHg at 25 °C, higher than most metals, facilitating at ambient conditions. Optically, mercury displays a metallic luster with reflectivity around 73% and a ranging from 1.6 to 1.9 at 20 °C, properties that historically enabled its use in mirrors despite chemical limitations. The coefficient of volume is approximately 182 × 10^{-6} /°C near , a value exploited in thermometers for precise volume-based temperature measurement due to its uniformity. In solid form, below its , mercury adopts a rhombohedral in the α phase at . Under high pressure, it undergoes phase transitions to denser allotropes: β phase above about 1 GPa, γ phase (monoclinic) around 2-6 GPa, and δ phase at higher pressures exceeding 10 GPa, reflecting compression-induced changes in atomic packing.

Chemical properties

Mercury exhibits low reactivity with most common reagents at ambient conditions, resisting oxidation by air or water and showing no reaction with dilute acids such as hydrochloric or . However, it dissolves in oxidizing acids like concentrated or , and particularly in —a 3:1 mixture of concentrated hydrochloric and s—yielding mercury(II) ions and complexes./22%3A_d-Block_Metal_Chemistry_-The_Heavier_Metals/22.13%3A_Group_12-_Cadmium_and_Mercury/22.13A%3A_The_Metals) This solubility in stems from the generation of nascent and , which facilitate oxidation to Hg(II). The element predominantly adopts +1 and +2 oxidation states, with the +1 state occurring as the dimeric Hg₂²⁺ ion rather than monomeric Hg⁺. This Hg(I) species is thermodynamically unstable, undergoing disproportionation via the reaction 2Hg₂²⁺ → 2Hg²⁺ + Hg(l), driven by the favorable formation of metallic mercury and the stability of the Hg²⁺ aquo complex./Qualitative_Analysis/Characteristic_Reactions_of_Select_Metal_Ions/Characteristic_Reactions_of_Mercury_Ions_(Hg_and_Hg)) Mercury's reluctance to form stable oxides contributes to its anomalous nobility among metals; elemental mercury does not tarnish in air and requires heating above 300°C in oxygen to produce mercury(II) oxide (HgO), which itself decomposes at around 500°C. Mercury readily forms amalgams—alloys with other metals such as , silver, sodium, and aluminum—owing to its low melting point and ability to dissolve these elements into its liquid matrix without requiring elevated temperatures. In electrochemical contexts, mercury displays reversible behavior, with the Hg²⁺/Hg couple exhibiting a standard reduction potential of +0.854 V versus the , reflecting its moderate oxidizing power compared to other . Its catalytic properties arise from surface adsorption capabilities, enabling facilitation of reactions like acetylene hydrochlorination in supported systems, though elemental mercury's inertness limits broad catalytic utility.

Isotopes

Mercury has seven stable isotopes, ranging from 196Hg to 204Hg, with 202Hg being the most abundant at approximately 29.65%. These isotopes contribute to the element's of 200.592(3) u, determined from weighted averages of their masses and natural abundances. The stable isotopes exhibit no observed , though theoretical predictions suggest potential instability for some over extremely long timescales.
IsotopeAtomic Mass (u)Natural Abundance (%)
196Hg195.96583(2)0.15(1)
198Hg197.966752(3)9.97(20)
199Hg198.968280(3)16.87(16)
200Hg199.968326(3)23.10(9)
201Hg200.970302(3)13.18(8)
202Hg201.970643(3)29.65(30)
204Hg203.973493(5)6.85(11)
Radioactive isotopes of mercury, such as 203Hg with a of 46.61 days, have been employed as tracers in to monitor mercury transport and fate in ecosystems. Neutron capture cross-sections for mercury isotopes, notably high for thermal neutrons (around 374 barns overall), influence their behavior in nuclear reactors and processes. Variations in stable isotopic ratios, particularly δ202Hg and Δ199Hg, enable studies for tracking mercury sources, distinguishing anthropogenic inputs like or from natural origins through mass-dependent and mass-independent signatures. These ratios reflect biogeochemical processes and have been applied to sediments, biota, and atmospheric samples for source apportionment.

History

Etymology

The name mercury for the element derives from the Roman god Mercury, the swift-footed messenger of the gods, a designation adopted by alchemists to evoke the metal's rapid liquidity and elusive mobility, qualities likened to the deity's agility in mythology. The element's chemical symbol, Hg, stems from the Latin hydrargyrum ("watery silver"), a direct romanization of the ancient Greek hydrargyros (ὑδράργυρος), compounding hydor ("water" or "liquid") and argyros ("silver") to describe its unique appearance as a dense, shiny fluid metal at standard conditions. This nomenclature persisted over alternatives like the English "quicksilver," from Old English cwicseolfor ("living silver"), emphasizing its vivacious flow and tendency to coalesce without solidification. In scientific systematization, Dmitri Mendeleev's 1869 periodic table classified mercury alongside and silver in a horizontal series, based on increasing atomic weights (mercury's then-estimated 200) and analogous chemical behaviors, thereby embedding its established name within a predictive framework of elemental periodicity.

Early history and

Mercury sulfide (cinnabar) served as a vibrant red pigment in ancient civilizations, with archaeological evidence indicating its application in decorative contexts dating to approximately years ago for coating walls, pottery, and burial sites. In , cinnabar provided the primary source of red pigment for artistic and cosmetic purposes, as identified in analyses of tomb decorations and artifacts from periods spanning the predynastic era onward. Chinese artisans employed mercury gilding techniques on bronze objects, mixing gold with liquid mercury to form amalgams that adhered effectively upon heating, a method favored for its minimal gold consumption and durability compared to foil wrapping. In Indian Ayurvedic traditions, mercury appeared in medical texts such as the , where it featured in topical applications for treating ailments, often processed into sulfide forms like rasasindur to purportedly mitigate while enhancing therapeutic effects. Greco-Roman sources, including Pliny the Elder's (circa 77 CE), detailed mercury's production via roasting ore and its practical utilities, such as forming amalgams for copper surfaces and extracting from ores by dissolution and recovery. Pliny also noted mercury's role in ointments, though he highlighted risks like during handling, based on empirical observations of workers' symptoms including salivation and skin irritation. Alchemical investigations intensified these empirical insights, with (circa 721–815 CE) formulating the sulfur-mercury theory, which posited that all metals arose from varying proportions of (conferring combustibility) and mercury (imparting metallic luster and fusibility), guiding experiments to replicate natural formation processes. This framework underpinned transmutation efforts, where alchemists heated mercury with base metals or gold, inadvertently isolating amalgam properties—mercury's ability to dissolve gold into a malleable —without achieving genuine elemental conversion, as verified by later chemical . Later, (1493–1541) integrated mercury into iatrochemical elixirs for treatment, administering it orally or topically to induce profuse salivation as a purported detoxifying sign, while documenting adverse effects like ulcers and systemic poisoning, attributing variability to dosage thresholds rather than inherent harmlessness. These pursuits revealed mercury's dual caustic and solvent behaviors through trial-and-error, prioritizing observable reactions over speculative mysticism.

Industrial era developments

In the early , mercury's unique liquid state at facilitated advancements in precision instrumentation. Evangelista Torricelli's 1643 invention of the laid groundwork for , but Daniel Fahrenheit's development of the in 1714 marked a pivotal industrial application, enabling accurate gauging superior to alcohol-based alternatives due to mercury's higher and density. This innovation, paired with Fahrenheit's eponymous scale formalized around 1724, spurred demand in scientific, meteorological, and manufacturing sectors, where consistent readings supported emerging industrial processes like and . Concurrently, mercury nitrate emerged in hat felting around 1720–1740, where it processed animal fur into felt by breaking down fibers, revolutionizing European hat production and fueling the fur trade's economic expansion despite early unrecognized health risks to workers. The saw mercury's role amplify in extractive industries, particularly through amalgamation for recovery. Building on the 16th-century , mercury's affinity for gold and silver enabled efficient ore processing; during the from 1849 onward, this method extracted vast quantities, with U.S. atmospheric emissions averaging 780 metric tons annually from 1850 to 1900, driving economic booms in mining regions like and . Parallel developments in introduced mercury cathodes in nascent chlor-alkali by the late 1800s, where flowing mercury amalgamated sodium from to produce caustic soda and —key chemicals for , , and disinfectants—enhancing industrial scalability as global chemical manufacturing expanded. These applications causally linked mercury supply chains to colonial mining outputs, with Spanish American silver operations losing hundreds of tons yearly to , underscoring the element's indispensable yet wasteful role in fueling 19th-century industrialization. By the , mercury dominated electrolytic processes, with chlor-alkali mercury cells becoming the largest consumer, accounting for substantial global production as chlorine demand surged for wartime explosives, PVC plastics, and pharmaceuticals post-World War I. However, the 1956 Minamata disaster in —where industrial discharge of mercury compounds into caused widespread , affecting over 2,000 people with neurological damage—highlighted environmental persistence and prompted initial regulatory scrutiny. Post-World War II, alternatives like diaphragm and cells in chlor-alkali production, alongside non-mercurial thermometers and cyanidation in , accelerated decline; commercial mercury use peaked around 1970 before sharp reductions driven by toxicity awareness and substitution technologies, though artisanal retained reliance on amalgamation for its simplicity in low-tech settings. This shift reflected causal trade-offs between mercury's efficiency in mass extraction and accumulating evidence of ecological and health externalities, reshaping industrial practices toward reduced dependence.

Occurrence and Production

Natural occurrence

Mercury occurs primarily in the Earth's crust as the sulfide mineral (HgS), which forms in low-temperature hydrothermal veins within volcanic and tectonically active regions. These deposits result from the mobilization and precipitation of mercury from deep crustal fluids, often linked to zones and magmatic activity that concentrate volatile elements like mercury. is typically brick-red and comprises up to 86% mercury by weight, making it the dominant mineral. Major concentrations are found in specific geological settings, such as the district in , which hosts the world's largest mercury deposit with stratabound mineralization in shales, and the Idrija mine in , associated with carbonates and hydrothermal alteration. These sites exemplify mercury's affinity for mercury-rich provinces formed by episodic fluid migration along faults and fractures in tectonically deformed terrains. The average abundance of mercury in the continental crust is approximately 0.08 ppm, reflecting its chalcophile nature and sequestration in sulfides rather than widespread dispersion. Trace quantities also exist as native elemental mercury (rarely) or in accessory minerals like metacinnabar (a cubic polymorph of HgS) and livingstonite (HgSb₄S₈), which occur in similar hydrothermal parageneses with and . Volcanic degassing contributes to diffuse atmospheric and oceanic mercury, releasing elemental vapor (Hg⁰) from mantle-derived magmas, though fluxes vary by eruption type and are estimated as the primary geogenic source globally. This process maintains baseline environmental levels independent of anthropogenic inputs.

Extraction methods

Mercury is primarily extracted from its ore (HgS) through thermal roasting, where the ore is heated in the presence of oxygen to decompose it into mercury vapor, gas, and residual oxides: HgS + O₂ → Hg(g) + SO₂. This volatilization occurs at temperatures around 500–600°C, leveraging mercury's low of 356.7°C to separate it from the solid matrix. In traditional methods, such as those refined at the mine in since Roman times and peaking in the 19th–20th centuries, concentrate was roasted in batch iron retorts—sealed vessels heated externally to drive off mercury vapors, which were then channeled through condensers for collection as . Recovery rates in these retort systems typically ranged from 90% to 95%, with losses primarily from incomplete volatilization or vapor escape, though yields could exceed 95% in optimized operations treating high-grade ores (e.g., 10 lb Hg per ton). Modern extraction employs continuous rotary or vertical furnaces for larger-scale processing, where crushed and concentrated is fed into a heated chamber, volatilizing mercury for subsequent and in cooled U-shaped tubes or electrostatic precipitators to yield purer liquid mercury. These systems improve by maintaining precise (up to 700°C) and integrating SO₂ scrubbing or conversion to , reducing gaseous emissions that historically contributed to local . Energy inputs are significant, often requiring or coke-fired heating, with overall recovery approaching 95–98% under controlled conditions. Mercury also arises as a byproduct during the roasting or of polymetallic ores in and lead , where trace HgS in concentrates volatilizes alongside primary metals and is captured via gas-phase or adsorption to prevent . In smelters, for instance, mercury content (often 10–50 ppm in feed) is removed by oxidative in controlled atmospheres, yielding recoverable Hg while minimizing redeposition. Key challenges include vapor losses from inadequate sealing or cooling in retorts, which can reach 0.2–0.4% per cycle and escalate in small-scale setups lacking ventilation controls, leading to occupational exposure and environmental release. Scaling for artisanal operations remains problematic due to high demands, inconsistent grades, and difficulties in SO₂ without industrial infrastructure, often resulting in lower yields (below 90%) and heightened emissions.

Global supply, demand, and illicit activities

Global mercury production in 2023 totaled approximately 2,100 metric tons, with accounting for 94.6% of output, followed by at 2.7% and . Annual production has declined from peaks exceeding 3,000 metric tons in prior years, driven by the Minamata Convention's phase-out of primary —banning new mines and limiting existing ones to 15 years post-ratification—along with reliance on existing stockpiles estimated at thousands of tons globally. By 2024, output stabilized around 2,000-2,200 metric tons, reflecting reduced activity in major producers amid international controls. Demand for mercury persists at roughly 2,000-3,000 metric tons annually, with artisanal and small-scale (ASGM) comprising the largest share—over 60% when combined with monomer (VCM) production—primarily in South and , , and . VCM processes, used in PVC , continue to drive industrial uptake despite phase-down mandates under the Minamata Convention, with robust consumption reported in as of 2024. Overall demand has not matched supply reductions, contributing to market surpluses projected through 2050 due to emission controls and declines. Illicit trade sustains mercury flows to unregulated sectors, particularly ASGM in the , where smuggling from to has escalated with high prices. In July 2025, Peruvian authorities seized a record 4 metric tons of black-market mercury en route from to for , highlighting a "-mercury-drug " involving cartels. An Environmental Investigation Agency report in July 2025 documented massive illegal shipments from polluting Amazon regions, with annual flows estimated in hundreds of tons evading Minamata trade restrictions. Mercury prices in Q2 2025 varied regionally, reaching approximately $47,000 per metric ton in parts of and amid supply gluts, though Indian spot prices hit $56,899 per metric ton by due to localized demand pressures. Forecasts indicate continued volatility but downward pressure from excess stockpiles and phase-outs, with global market value projected to grow modestly at 1% CAGR through 2032.

Chemistry

Reactivity and bonding

Mercury's is characterized by weak interatomic interactions, primarily attributable to relativistic effects on its 6s electrons. These effects cause a contraction of the 6s orbitals due to increased velocities near the heavy nucleus, enhancing the and stabilizing the lone-pair electrons, which results in reduced orbital overlap with adjacent atoms and diminished cohesive forces. This lability in contrasts with stronger metallic bonds in neighboring elements like , contributing to mercury's chemical despite its position in the periodic table. The nobility of elemental mercury is quantified by the standard reduction potential of the Hg²⁺/Hg couple, approximately +0.85 V, indicating resistance to oxidation under standard conditions. This high potential arises from the relativistic stabilization of the 6s² configuration, akin to the observed in post-transition metals, which disfavors the loss of both valence electrons to form Hg²⁺. In Lewis acid-base interactions, mercury behaves as a soft acid per the hard-soft acid-base (HSAB) theory, exhibiting preferential affinity for soft donor atoms such as sulfur over harder ones like oxygen. This selectivity stems from the polarizable, low-charge-density nature of Hg²⁺ and Hg⁺, favoring covalent bonding with polarizable ligands through mechanisms like back-donation and dispersion forces. Mercury's reactivity is further influenced by its volatility, with a vapor pressure of about 0.0012 at 20°C, enabling facile evaporation and participation in gas-phase or coordination processes. This property facilitates the transport of mercury atoms or clusters in vapor form, where relativistic effects similarly weaken intermolecular forces, promoting monomeric behavior over clustering.

Mercury(I) compounds

Mercury(I) compounds contain the [Hg₂]²⁺ cation, a homodimeric formed by two mercury atoms connected via a single covalent Hg–Hg bond, distinguishing it from mononuclear mercury ions. This cation arises from the weak oxidizing power of Hg⁺, which favors dimerization over independent monocation stability, with the bonding primarily involving overlap of 6s orbitals from each mercury atom. The [Hg₂]²⁺ ion adopts a linear geometry, as evidenced by X-ray diffraction studies showing Hg–Hg bond lengths of 2.50 Å in crystalline salts and approximately 2.52 Å in perchlorate solutions. This bond length reflects partial single-bond character, longer than in neutral Hg₂ (200 pm) but shorter than van der Waals distances, confirming covalent interaction. In aqueous media, [Hg₂]²⁺ undergoes reversible disproportionation: Hg₂²⁺ ⇌ Hg(l) + Hg²⁺, with the equilibrium constant K ≈ 1.6 × 10⁻² at 25°C, favoring the undissociated form but allowing detectable mercury metal precipitation under certain conditions like excess ligands or reducing agents. This instability limits solubility of many mercury(I) salts, promoting precipitation as a stabilization mechanism; for instance, mercury(I) nitrate disproportionates readily, while halides resist due to low lattice energies. A prototypical stable mercury(I) compound is mercury(I) chloride (Hg₂Cl₂, calomel), which precipitates as white, odorless crystals with tetrahedral morphology and negligible water solubility (0.2 mg/100 mL at 20°C), corresponding to a Ksp of approximately 1.4 × 10⁻¹⁸. Calomel forms via comproportionation of Hg(0) and HgCl₂ or electrolytic reduction of Hg(II), and its insolubility made it suitable for historical medicinal applications and modern use in calomel electrodes for pH measurements, where the half-cell reaction Hg₂Cl₂ + 2e⁻ ⇌ 2Hg + 2Cl⁻ establishes a stable potential. Similar sparingly soluble halides include Hg₂Br₂ (yellow) and Hg₂I₂ (greenish-yellow), which exhibit analogous linear Cl–Hg–Hg–Cl or equivalent units in their crystal structures, with precipitation behaviors exploited in qualitative analysis to distinguish mercury ions from other metals. Spectroscopic methods confirm the [Hg₂]²⁺ structure; reveals a characteristic Hg–Hg stretching vibration at 110–170 cm⁻¹, as observed in Hg₂I₂ (110 cm⁻¹) and derivatives, with the band's intensity and position sensitive to anion coordination and phase. spectra of these compounds show weak or absent Hg–Hg modes due to , but ligand vibrations (e.g., C–O stretches in carboxylates) shift upon coordination, aiding identification. Synthetic access to pure mercury(I) species remains challenging, often requiring inert atmospheres or non-aqueous solvents to suppress , with complexes like [Hg₂(phen)₄]²⁺ (phen = ) stabilized by despite eventual decomposition.

Mercury(II) compounds

Mercury(II) compounds feature the Hg²⁺ cation, a soft Lewis acid that preferentially binds soft bases like sulfur and iodide, forming predominantly covalent bonds with linear or tetrahedral coordination geometries./Qualitative_Analysis/Characteristic_Reactions_of_Select_Metal_Ions/Characteristic_Reactions_of_Mercury_Ions_(Hg%5E2%2B_and_Hg_2%5E2%2B)) This affinity is evident in complexes with halides and cyanides; for instance, mercury(II) chloride (HgCl₂) adopts a linear covalent structure, while mercury(II) iodide (HgI₂) forms a polymeric network of edge-sharing HgI₄ tetrahedra, resulting in a red crystalline solid. Mercury(II) sulfide (HgS), known as cinnabar in its natural form, exists in black (α-HgS) and red (β-HgS, vermilion) polymorphs, with the latter prized as a stable red pigment due to its insolubility and resistance to oxidation. In aqueous solutions, Hg²⁺ forms aquo complexes that readily hydrolyze, yielding species such as HgOH⁺ and polymeric hydroxo complexes, particularly at pH > 3, leading to precipitation of basic mercury(II) salts or oxides. Stability constants for Hg²⁺ complexes vary widely but are notably high for soft ligands; for example, log K values for Hg²⁺ with amino acids and thiols can exceed 20, reflecting strong thermodynamic favorability, while phosphate complexes like HgHPO₄ have solubility products around log K_s = -13.1. Cyanide forms highly stable tetrahedral [Hg(CN)₄]²⁻, underscoring the ion's class B behavior in coordination chemistry. Analytical precipitation tests exploit these properties: addition of sulfide ions yields black HgS, iodide produces scarlet HgI₂ (soluble in excess iodide as [HgI₄]²⁻), and alkali hydroxides precipitate yellow HgO alongside finely divided mercury metal from partial reduction./Qualitative_Analysis/Characteristic_Reactions_of_Select_Metal_Ions/Characteristic_Reactions_of_Mercury_Ions_(Hg%5E2%2B_and_Hg_2%5E2%2B)) These reactions provide qualitative confirmation of Hg²⁺ in the presence of other cations, with color and solubility distinctions aiding differentiation from mercury(I) species. Thermal decomposition patterns of mercury(II) compounds typically involve reduction to elemental mercury and liberation of the anion or oxygen; mercury(II) oxide (HgO), a red or yellow solid, decomposes above 400 °C via 2HgO → 2Hg + O₂, a process historically used by Priestley in 1774 to isolate oxygen./11:_Chemical_Reactions/11.05:_Decomposition_Reactions) Similarly, HgS decomposes at 265–345 °C following first-order kinetics to Hg(g) + S, while halides like HgCl₂ sublime or decompose to Hg and Cl₂ at elevated temperatures. These decompositions highlight the relative instability of the +2 oxidation state under heat, driven by the favorable formation of metallic mercury.

Organomercury compounds

Organomercury compounds contain at least one carbon-mercury bond and are classified primarily into alkylmercury (e.g., dialkylmercury R₂Hg or alkylmercury salts RHgX) and arylmercury (e.g., ArHgX) derivatives, with alkyl types exhibiting greater volatility and lipophilicity compared to aryl analogs. Symmetrical dialkylmercury compounds are synthesized by reacting two equivalents of alkyl halide with mercury metal in the presence of sodium, or via Grignard reagents: 2 RMgX + HgX₂ → R₂Hg + MgX₂ (after hydrolysis). Arylmercury salts are prepared through electrophilic mercuration of aromatic rings with mercury(II) acetate, yielding ArHgOAc, or via organolithium procedures analogous to alkyl methods. Methylmercury chloride (CH₃HgCl), a prototypical alkylmercury compound, features a linear structure with the methyl group bonded to Hg⁺, and can be laboratory-prepared from methyl Grignard reagents or reduction of Hg(II) salts with methyl donors. The mercury-carbon bond in organomercury compounds displays significant covalent character, polarized by the electronegativity difference (carbon 2.55, mercury 2.00), which imparts resistance to hydrolysis in aqueous media while maintaining monomeric structures for dialkyl species as colorless, air-stable liquids or low-melting solids. This bond stability contrasts with sensitivity to ultraviolet light, where photolysis cleaves C-Hg linkages, and to halogens, which exchange to form organic halides via oxidative addition. Alkylmercury compounds, particularly short-chain variants like methylmercury, act as precursors for bioaccumulative forms due to the persistence of the C-Hg bond under physiological conditions, facilitating their role in biomolecular interactions. In synthetic applications, mercury(II) salts enable oxymercuration, a catalytic process for functionalization: alkenes react with Hg(OAc)₂ in water or alcohol to form β-hydroxymercury or β-alkoxymercury acetates via a mercurinium intermediate, followed by demercuration with NaBH₄ to yield Markovnikov alcohols or ethers without rearrangements. This stereospecific anti-addition mechanism exploits the electrophilicity of Hg(II), with the reaction proceeding under mild conditions (typically 20-50°C) and tolerating various substituents, though arylmercury intermediates are less common than alkyl in such transformations.

Applications

Industrial manufacturing

Mercury's primary industrial application in manufacturing has been as a cathode in the chlor-alkali electrolysis process for producing chlorine and sodium hydroxide. In this configuration, brine is electrolyzed with mercury serving as the cathode, forming a sodium amalgam that is reacted with water to yield high-purity caustic soda with chloride content below 50 ppm, far superior to the 100-200 ppm typical of diaphragm cells. Cathodic current efficiencies reached 94-96%, minimizing energy losses from hydrogen evolution and enabling reliable large-scale output, though overall energy use averaged 3,200-3,400 kWh per metric ton of Cl₂, higher than modern alternatives due to amalgam decomposition requirements. This purity advantage reduced downstream processing costs by up to 20% in applications like rayon production, offsetting higher electricity demands compared to pre-membrane technologies. The Reppe process utilized mercury(II) sulfate catalysts for acetylene hydration to acetaldehyde, operating at 90-100°C and 1-2 atm to achieve yields exceeding 90%, which provided economic superiority over thermal direct hydration methods requiring higher temperatures and pressures. Catalyst loadings of 0.5-1% Hg by weight enabled cost-effective operation when acetylene derived from inexpensive calcium carbide, with production costs estimated 15-25% lower than competing routes in the 1940s-1950s due to process simplicity and minimal byproducts. However, the rise of ethylene oxidation (Wacker process) post-1950s, leveraging cheaper petrochemical feedstocks, rendered Reppe uneconomical, as ethylene-based acetaldehyde costs dropped below $0.20/kg by the 1960s versus Reppe's $0.30-0.40/kg equivalents adjusted for era. Global phase-outs under the Minamata Convention have curtailed these uses, mandating mercury elimination in chlor-alkali by 2025 and catalysis by 2018, with cells now dominating via lower energy (2,500-2,800 kWh/ Cl₂) and zero mercury emissions, though conversion exceed $500/annual capacity. Residual mercury-cell capacity persists in developing regions, including two plants holding ~100 tons of mercury as of 2024, where retrofits lag due to and constraints, sustaining ~5-10% of global chlor-alkali output in non-compliant facilities. mercury catalysis is similarly obsolete industrially, with no significant reported volumes post-2018 outside legacy or artisanal contexts.

Laboratory and analytical uses

Mercury thermometers provide precise measurements in settings, achieving accuracies of ±0.01°C through mercury's linear coefficient of of approximately 0.00018 per °C, which minimizes non-linear errors in scales. These instruments have historically served as secondary standards for calibrating other thermometric devices, with immersion depths standardized to ensure reproducibility across -200°C to 600°C ranges. Mercury barometers enable absolute pressure measurements with uncertainties as low as 0.1 mmHg, relying on the element's of 13.534 g/cm³ at 0°C and its low to isolate gravitational effects from atmospheric influences. In laboratory metrology, they function as primary references for verifying aneroid and digital barometers, with corrections applied for temperature-induced variations using the ρ = ρ₀ [1 - β(T - T₀)], where β is the cubical expansion coefficient. In electrochemical analysis, the dropping mercury electrode (DME) facilitates , a voltammetric method for detecting trace concentrations (down to 10⁻⁶ M) of reducible like , by providing a continuously renewed electrode surface that avoids adsorption artifacts. The DME operates via capillary extrusion of mercury droplets at rates of 1-2 mg/s, yielding diffusion-limited currents proportional to concentration per Ilkovich's equation: i_d = 607 n D^{1/2} m^{2/3} t^{1/6} C, where n is electrons transferred, D is , m is mass flow rate, t is drop time, and C is concentration. The (SCE), comprising a pool of mercury in contact with Hg₂Cl₂ paste and saturated KCl solution, delivers a stable reference potential of +0.244 V vs. at 25°C, essential for potentiometric and voltammetric setups in and ion-selective measurements./Analytical_Sciences_Digital_Library/Courseware/Analytical_Electrochemistry:_Potentiometry/03_Potentiometric_Theory/04_Reference_Electrodes) Its half-cell reaction, Hg₂Cl₂ + 2e⁻ ⇌ 2Hg + 2Cl⁻, ensures minimal polarization due to high at the mercury interface./Analytical_Sciences_Digital_Library/Courseware/Analytical_Electrochemistry:_Potentiometry/03_Potentiometric_Theory/04_Reference_Electrodes) Mercury-based McLeod gauges measure low pressures (10⁻³ to 10⁻⁶ ) by trapping and compressing gas samples into a via mercury displacement, providing absolute readings independent of gas composition and serving as standards for and Pirani gauges. The pressure P is calculated as P = (V_c / V_m) * (h * ρ * ), where V_c and V_m are capillary and volumes, h is mercury difference, ρ is mercury density, and g is , with superior performance over liquid metal alternatives like owing to mercury's below 10⁻³ at .

Mining and extraction aids

Mercury amalgamation remains a primary method in artisanal and small-scale (ASGM) for extracting from placer deposits and low-grade ores, where liquid mercury binds with fine particles to form an that can be separated from materials. This process enables recovery of particles too small for effective concentration, with reported rates often reaching or exceeding 90% in rudimentary operations suited to placer deposits. In contrast, alternatives such as cyanidation demand controlled chemical handling, management, and disposal infrastructure, which prove less viable in remote, low-capital ASGM settings lacking technical expertise or regulatory oversight. ASGM accounts for the predominant demand for mercury in , with global usage estimated at approximately 2094 tonnes per year as of recent assessments, predominantly driving informal economic activity in resource-dependent regions like and the . In these areas, mercury-based extraction sustains livelihoods for millions, contributing substantially to local and national outputs amid limited formal employment alternatives. The Minamata Convention on Mercury mandates reductions in ASGM mercury use, promoting technologies like retorts that capture and condense mercury vapors during amalgam burning, achieving emissions reductions of at least 90% compared to open-air methods. Despite such interventions, phase-out efforts encounter persistent hurdles, including miners' economic reliance on high-yield amalgamation, resistance to unproven alternatives yielding lower recoveries in practice, and enforcement gaps in informal sectors. Successful transitions often hinge on subsidized equipment, training, and viable mercury-free processes tailored to local ore types, though adoption remains uneven as of 2025.

Other specialized uses

Mercury(II) fulminate served as a key primary in firearm primers, enabling reliable upon impact in percussion caps introduced in 1828 and persisting in early centerfire cartridges through the late . Its sensitivity to shock provided consistent ignition, though mercury release embrittled cases, leading to replacement by non-mercuric compounds; residual use continues in certain Eastern Bloc-manufactured . In neon sign fabrication, trace mercury (typically 50-150 mg per tube) is introduced into argon-neon mixtures to intensify emission spectra via vapor excitation, yielding brighter blues and purples compared to gas-only fills. Specialized electrodes encapsulate up to 88 mg of liquid mercury in capsules to sustain arc stability and prevent . Dental amalgams, formulated with 43-54% elemental mercury alloyed to silver, tin, , and , offered exceptional longevity—often exceeding 10-15 years in posterior restorations—due to low wear and matching . Phased out in the by January 1, 2025, for environmental reasons, their mechanical durability supported widespread adoption until alternatives like composites gained viability. Inorganic mercury salts in skin lightening creams, such as ammoniated mercury at 1-10% concentrations, potently inhibit enzyme activity, reducing synthesis for measurable within weeks of application. This efficacy stems from mercury's affinity for sulfhydryl groups in melanocytes, though transdermal absorption limits long-term . Mercury-based processes produce alkali alcoholates, which catalyze in synthesis by facilitating methanolysis of triglycerides at yields up to 98% under mild conditions. High-purity mercury sustains these and other marginal sectors, with global niche demand valued at approximately $0.1 billion in 2025.

Toxicology

Mechanisms of action

Mercury exerts toxicity primarily through its role as a soft Lewis acid, exhibiting high affinity for soft nucleophilic sites such as the thiol groups (-SH) in residues of proteins and enzymes, thereby disrupting their structure and function. This binding inhibits critical enzymatic activities, including those involved in cellular , by forming stable mercaptide bonds that alter protein conformation and block active sites. Inorganic mercury species, such as Hg²⁺, and organic forms like (MeHg⁺), both target thiol-containing biomolecules, with MeHg forming a complex (MeHg-cys) that mimics and facilitates cellular uptake via large neutral transporters (LAT1). This mechanism enables MeHg to cross the blood-brain barrier, where it accumulates and binds to neuronal proteins, exacerbating through sustained inhibition. These interactions trigger oxidative stress by depleting glutathione (GSH) and generating reactive oxygen species (ROS), which damage lipids, proteins, and DNA via peroxidation and further thiol oxidation. Mercury's interference with antioxidant enzymes, such as glutathione peroxidase, amplifies ROS production, creating a feedback loop of cellular damage independent of initial binding sites. Dose-response relationships for these mechanisms show low thresholds for adverse effects; for instance, a LOAEL of 0.015 mg Hg/kg/day for MeHg has been identified in models for renal and developmental perturbations linked to binding and oxidative imbalance. Benchmark dose modeling from human cohorts further supports neurodevelopmental risks at chronic exposures around 0.01-0.028 mg/kg/day, reflecting cumulative protein dysfunction.

Human health effects

Exposure to elemental mercury vapor primarily occurs through inhalation, with acute high-level exposure causing pneumonitis characterized by fever, chills, cough, chest pain, and shortness of breath, potentially progressing to severe respiratory distress and death from hypoxia. Chronic low-level inhalation leads to neurological symptoms including tremors, paresthesia, memory loss, insomnia, headaches, and cognitive dysfunction, often accompanied by gingivitis and erethism (irritability and excitability), historically termed Mad Hatter's syndrome or erethism mercurialis due to its observation in 19th-century hatters exposed to mercury vapors during felt processing. Inorganic mercury compounds, typically ingested or absorbed dermally, induce acute gastrointestinal corrosion with symptoms of severe , , , bloody , and , alongside systemic effects like renal tubular and . Chronic exposure manifests as progressive renal failure, , and with motor deficits and . Organic mercury, particularly , exerts profound , with acute poisoning causing , , , visual and hearing impairment, and in severe cases, and death; chronic exposure results in persistent sensory disturbances, , and as seen in , where epidemiological surveys identified , numbness, and peripheral vision loss in affected populations from the 1950s outbreak. The 1971 Iraq outbreak from consumption of methylmercury-treated grain hospitalized 6,530 individuals and caused 459 deaths, predominantly among children under 10, with survivors exhibiting delayed neurological sequelae including tremors and developmental delays. Fetotoxicity from prenatal exposure is evidenced by , , and neurodevelopmental deficits, including reduced IQ; cohort studies like the Faroe Islands research link maternal hair mercury levels above 10-15 ppm to a 2-7 point IQ decrement in offspring. Meta-analyses confirm associations between blood mercury concentrations of 5-20 µg/L and subtle cognitive impairments, though at lowest observed levels remains debated due to factors in observational data. Epidemiological thresholds indicate no observed levels around 0.1 µg/kg body weight/day for , corresponding to blood concentrations below 5-6 µg/L, beyond which risks of escalate, as derived from benchmark dose modeling in and Faroe cohorts; recent studies affirm overt effects above 50 µg/L but highlight subclinical risks at 10-20 µg/L without a clear safe threshold for sensitive populations like fetuses.

Exposure routes and biomagnification

Human exposure to mercury occurs primarily through three routes: of mercury vapor, of via contaminated food, and to a lesser extent, dermal contact with inorganic forms. represents the dominant pathway for mercury, with approximately 80% of inhaled vapor absorbed through the due to its high volatility and , facilitating rapid into the bloodstream. Dermal absorption of mercury is minimal, estimated at around 2% of the equivalent inhaled dose during prolonged skin contact, as the metal's low in limits penetration through intact . Dietary intake of , the most bioavailable organic form, predominantly arises from consuming species that accumulate it through aquatic food webs, such as and . The U.S. and Environmental Protection Agency advise limiting consumption of high-mercury fish like , , , and to reduce intake, as these species often exceed 0.5–1.0 ppm mercury, with averaging 0.689 ppm and similarly elevated. 's (log K_ow ≈ 1.6–2.0) contributes to its uptake and retention in lipid-rich tissues, though drives higher concentrations in top predators. Methylmercury exhibits strong in aquatic and terrestrial food chains, increasing concentrations by a factor of 3–6 times per as it transfers from primary producers to herbivores and predators, with trophic magnification factors (TMF) for total mercury often ranging 1.5–8.3 in freshwater and marine systems. This process amplifies exposure risks for humans at higher trophic positions, particularly through piscivorous diets. Occupational exposure in artisanal small-scale (ASGM) communities, where elemental mercury is used for amalgamation, results in mercury levels 10–100 times above background concentrations (typically <1 µg/L), with medians reported up to 7–109 µg/L and maxima exceeding 600 µg/L in affected populations.

Treatment protocols

Treatment of mercury poisoning emphasizes immediate removal from the exposure source to prevent further absorption, as this constitutes the primary intervention across all forms. Supportive care addresses acute symptoms, such as providing or oxygen for respiratory distress following elemental mercury vapor inhalation, which can induce . measures, including for recent ingestion or whole-bowel irrigation for solid forms, may be employed if presentation occurs within hours, though efficacy diminishes rapidly due to mercury's rapid absorption. Chelation therapy targets inorganic and mercury poisoning to enhance excretion, with dimercaptosuccinic acid (DMSA, or succimer) and 2,3-dimercaptopropane-1-sulfonate (DMPS) as preferred agents over historical options like British anti-Lewisite (BAL, or ). BAL, developed in the initially for exposure, was used from the for mercury via intramuscular administration but carries risks of redistribution to the and lower . In contrast, oral DMSA at doses up to 30 mg/kg/day increases urinary mercury excretion and reduces tissue levels without significant redistribution, showing superiority in animal models for removal compared to other dithiols. DMPS similarly boosts excretion but requires caution due to potential interference with selenium-mediated protection when co-administered. For mercury, is initiated if blood levels exceed 40-50 µg/L or symptoms persist post-decontamination. Organic mercury compounds, particularly alkyl forms like , lack a specific , with chelators offering limited benefit due to poor blood-brain barrier penetration and potential for incomplete elimination. DMSA modestly lowers blood concentrations in low-exposure cases but does not reverse neurological once established. Adjunctive approaches, such as N-acetylcysteine, have been explored to accelerate excretion but remain investigational without proven superiority over supportive measures alone. Post-treatment follow-up involves serial monitoring of mercury levels via (for inorganic/ forms), (for recent organic exposure), and (for chronic assessment), with analysis guiding duration and assessing residual risk. Clinical trials indicate DMSA regimens of 19-30 days can sustain reduced levels, though long-term neurological surveillance is essential given irreversible effects in severe cases.

Environmental Impact

Emission sources and cycles

Anthropogenic sources dominate primary mercury emissions to the atmosphere, contributing an estimated 50-70% of the global total, with artisanal and small-scale (ASGM) accounting for approximately 37% and for 24% of anthropogenic releases. Natural geogenic sources, including volcanic activity and geological , contribute 10-20%, while re-emissions from previously deposited mercury in soils and form a significant secondary flux that has increased from about 44% of atmospheric inputs in 2010 to 62% in 2020. Global anthropogenic emissions are estimated at around 2,220 metric tons per year, though models incorporating re-emission loops indicate higher total fluxes due to evasion from surfaces and terrestrial reservoirs. Elemental mercury (Hg⁰), the predominant atmospheric form, exhibits a of 6-12 months, enabling long-range transport before deposition via wet and dry processes to soils, , and . Deposited mercury undergoes in anaerobic sediments and soils, facilitating , but a substantial portion re-enters the atmosphere through volatilization driven by microbial activity, , and solar , creating persistent biogeochemical loops. Ocean burial accounts for roughly half of the global mercury inventory, primarily in deep sediments, where reduced re-emission occurs due to burial efficiency exceeding 90% in coastal and marginal seas. Terrestrial soils, particularly those contaminated by legacy emissions near former industrial sites, serve as net sources via photoreduction and evasion, with models showing subsurface migration and re-emission sustaining elevated atmospheric levels for decades post-emission cessation. Monitoring from global networks, including high-altitude sites like , reveals a approximately 70% decline in atmospheric mercury concentrations from 2005 to 2025, attributed to reduced primary anthropogenic inputs outweighing re-emission contributions. analyses confirm that while primary emissions have decreased, the legacy pool—encompassing historical anthropogenic deposits—now drives a growing fraction of the cycle, with and re-emissions amplifying hemispheric transport patterns. These dynamics underscore the inertia in mercury's global flux, where short-term emission reductions yield observable atmospheric improvements, but long-term sequestration in sinks like sediments is essential for stabilizing inventories.

Monitoring and remediation

Monitoring of mercury in environmental media relies on speciation analysis to distinguish elemental, inorganic, and methylmercury forms, as bioavailability and toxicity vary by species. Cold vapor atomic fluorescence spectroscopy (CVAFS) is a primary technique, achieving detection limits as low as 0.01 ng/L with pre-concentration for water samples. This method involves reduction to elemental mercury vapor followed by fluorescence detection, enabling quantification at trace levels in air, water, and soil. For small-scale spills of mercury, initial containment uses absorbent materials to collect droplets, followed by application of sulfur powder, which forms mercuric to immobilize residues and reduce vapor emissions. Amalgamation with or proprietary powders then binds remaining mercury into collectible forms, preventing re-volatilization during cleanup. These protocols minimize airborne exposure but require ventilation and , with post-cleanup verification via CVAFS to confirm levels below 0.1 µg per wipe. Remediation of mercury-contaminated sediments often employs capping with clean material to isolate pollutants from the , proving more cost-effective than for shallow sites due to lower mobilization risks and disposal costs. removes sediments mechanically but incurs high expenses from excavation, treatment, and off-site disposal, with effectiveness depending on site depth and mercury concentration. Both methods reduce bioavailable mercury, though capping achieves containment without disturbing overlying water, limiting secondary contamination. Phytoremediation uses plants like in pilot-scale wetlands to uptake mercury from water and sediments, with field trials demonstrating up to 96% removal efficiency in controlled systems over several weeks. and monocultures or mixtures have shown 81-96% reductions in aqueous mercury, leveraging root adsorption and translocation, though scalability is limited by plant management and seasonal variability. These approaches offer low-cost alternatives for diffuse contamination but require monitoring to prevent re-release of bioaccumulated mercury. Activated carbon filters, often sulfur-impregnated, capture mercury from water and flue gases via adsorption, achieving 81-98% removal efficiencies depending on contact time and loading. In 2024-2025 developments, advanced sorbents like modified carbon nanotubes and metal oxide composites enhance flue gas capture to over 90%, with improved sulfur and water resistance reducing operational costs compared to traditional injectors. These sorbents target elemental mercury in coal-fired emissions, balancing high capacity (up to 289 mg/g) against regeneration challenges for long-term viability.

Regulatory measures and effectiveness

The , adopted on October 10, 2013, and entered into force on August 16, 2017, establishes a framework for over 140 parties to reduce global mercury emissions through measures including the phase-down of mercury use in artisanal and small-scale (ASGM), supply source controls, and product phase-outs. Article 7 specifically mandates national plans to reduce mercury in ASGM, where it remains the dominant anthropogenic emission source exceeding 2,000 tonnes annually. In the , the revised Regulation on Mercury, entering into force on July 30, 2024, bans the remaining intentional uses of mercury, such as in dental amalgams effective , 2025, and certain lamps by 2026, aligning with zero-pollution goals and Minamata obligations. The ' Mercury and Air Toxics Standards (MATS), finalized in 2012, impose emission limits on - and oil-fired power plants; in June 2025, the EPA proposed repealing 2024 amendments to these standards, which could relax non-mercury toxic controls while retaining core mercury limits. Canada's amended Products Containing Mercury Regulations, effective June 19, 2025, prohibit imports and manufacture of mercury-added products lacking alternatives, with progressive bans on common lamp types through 2030. Transboundary trade is restricted under the , which classifies elemental mercury and compounds as hazardous wastes subject to prior for movements, with amendments enhancing controls on mercury-contaminated e-waste since 2019. These frameworks have driven a nearly 70% reduction in atmospheric mercury concentrations over the past two decades, attributable to curtailed industrial emissions in developed regions. Compliance data indicate substantial progress in regulated sectors, yet ASGM evasion through informal operations undermines effectiveness, sustaining over one-third of global anthropogenic releases despite phase-down mandates.

Debates on policy efficacy

Technological interventions, such as wet scrubbers on coal-fired power plants, have achieved significant mercury emission reductions, with capture rates of 36% to 90% for combustion. In , retrofitting measures from 2011 to 2015 reduced emissions by 23.51 tons, averting an estimated 114 premature deaths and preserving 30,484 IQ points. Proponents of stringent controls, including supporters of the Minamata Convention, argue these outcomes demonstrate policy efficacy in curbing anthropogenic releases, which constitute about 30% of total atmospheric mercury inputs, with the balance from natural sources like re-emissions and geogenic fluxes. Critics contend that such regulations impose disproportionate economic burdens, particularly on artisanal and small-scale (ASGM), where mercury amalgamation extracts vital for livelihoods in developing regions, often yielding higher short-term economic returns than health costs from exposure. Blanket phase-outs under frameworks like Minamata overlook ASGM's role in producing up to 20% of global supply, exacerbating without viable alternatives like leaching, which carries its own environmental risks. Post-Convention smuggling has surged, with approximately 200 tons trafficked to the from 2019 to mid-2025, and global mercury trade volumes rising 40% to 1,700 tons in 2022, undermining emission goals while sustaining informal . Economic projections highlight supply-demand imbalances from supply-side restrictions, forecasting a global excess mercury stock of 14,439 to 20,943 tons by 2050 under Minamata scenarios, assuming varying recovery rates. Advocates for targeted interventions—focusing on high-impact sectors like while permitting controlled ASGM use with remediation—argue this avoids stifling industrial development in low-income areas, where natural mercury fluxes already dominate local cycles and alarmist anthropogenic-focused narratives inflate policy costs relative to benefits. Such approaches prioritize causal trade-offs, recognizing that abrupt bans drive black markets without reducing net emissions, as evidenced by persistent ASGM mercury demand exceeding formal supply curbs.

References

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