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Mercury (element)

gold ← Mercury → thallium
Cd

Hg

Uub
Element 1: Hydrogen (H), Other non-metal
Element 2: Helium (He), Noble gas
Element 3: Lithium (Li), Alkali metal
Element 4: Beryllium (Be), Alkaline earth metal
Element 5: Boron (B), Metalloid
Element 6: Carbon (C), Other non-metal
Element 7: Nitrogen (N), Other non-metal
Element 8: Oxygen (O), Other non-metal
Element 9: Fluorine (F), Halogen
Element 10: Neon (Ne), Noble gas
Element 11: Sodium (Na), Alkali metal
Element 12: Magnesium (Mg), Alkaline earth metal
Element 13: Aluminium (Al), Other metal
Element 14: Silicon (Si), Metalloid
Element 15: Phosphorus (P), Other non-metal
Element 16: Sulfur (S), Other non-metal
Element 17: Chlorine (Cl), Halogen
Element 18: Argon (Ar), Noble gas
Element 19: Potassium (K), Alkali metal
Element 20: Calcium (Ca), Alkaline earth metal
Element 21: Scandium (Sc), Transition metal
Element 22: Titanium (Ti), Transition metal
Element 23: Vanadium (V), Transition metal
Element 24: Chromium (Cr), Transition metal
Element 25: Manganese (Mn), Transition metal
Element 26: Iron (Fe), Transition metal
Element 27: Cobalt (Co), Transition metal
Element 28: Nickel (Ni), Transition metal
Element 29: Copper (Cu), Transition metal
Element 30: Zinc (Zn), Transition metal
Element 31: Gallium (Ga), Other metal
Element 32: Germanium (Ge), Metalloid
Element 33: Arsenic (As), Metalloid
Element 34: Selenium (Se), Other non-metal
Element 35: Bromine (Br), Halogen
Element 36: Krypton (Kr), Noble gas
Element 37: Rubidium (Rb), Alkali metal
Element 38: Strontium (Sr), Alkaline earth metal
Element 39: Yttrium (Y), Transition metal
Element 40: Zirconium (Zr), Transition metal
Element 41: Niobium (Nb), Transition metal
Element 42: Molybdenum (Mo), Transition metal
Element 43: Technetium (Tc), Transition metal
Element 44: Ruthenium (Ru), Transition metal
Element 45: Rhodium (Rh), Transition metal
Element 46: Palladium (Pd), Transition metal
Element 47: Silver (Ag), Transition metal
Element 48: Cadmium (Cd), Transition metal
Element 49: Indium (In), Other metal
Element 50: Tin (Sn), Other metal
Element 51: Antimony (Sb), Metalloid
Element 52: Tellurium (Te), Metalloid
Element 53: Iodine (I), Halogen
Element 54: Xenon (Xe), Noble gas
Element 55: Caesium (Cs), Alkali metal
Element 56: Barium (Ba), Alkaline earth metal
Element 57: Lanthanum (La), Lanthanoid
Element 58: Cerium (Ce), Lanthanoid
Element 59: Praseodymium (Pr), Lanthanoid
Element 60: Neodymium (Nd), Lanthanoid
Element 61: Promethium (Pm), Lanthanoid
Element 62: Samarium (Sm), Lanthanoid
Element 63: Europium (Eu), Lanthanoid
Element 64: Gadolinium (Gd), Lanthanoid
Element 65: Terbium (Tb), Lanthanoid
Element 66: Dysprosium (Dy), Lanthanoid
Element 67: Holmium (Ho), Lanthanoid
Element 68: Erbium (Er), Lanthanoid
Element 69: Thulium (Tm), Lanthanoid
Element 70: Ytterbium (Yb), Lanthanoid
Element 71: Lutetium (Lu), Lanthanoid
Element 72: Hafnium (Hf), Transition metal
Element 73: Tantalum (Ta), Transition metal
Element 74: Tungsten (W), Transition metal
Element 75: Rhenium (Re), Transition metal
Element 76: Osmium (Os), Transition metal
Element 77: Iridium (Ir), Transition metal
Element 78: Platinum (Pt), Transition metal
Element 79: Gold (Au), Transition metal
Element 80: Mercury (Hg), Transition metal
Element 81: Thallium (Tl), Other metal
Element 82: Lead (Pb), Other metal
Element 83: Bismuth (Bi), Other metal
Element 84: Polonium (Po), Other metal
Element 85: Astatine (At), Halogen
Element 86: Radon (Rn), Noble gas
Element 87: Francium (Fr), Alkali metal
Element 88: Radium (Ra), Alkaline earth metal
Element 89: Actinium (Ac), Actinoid
Element 90: Thorium (Th), Actinoid
Element 91: Protactinium (Pa), Actinoid
Element 92: Uranium (U), Actinoid
Element 93: Neptunium (Np), Actinoid
Element 94: Plutonium (Pu), Actinoid
Element 95: Americium (Am), Actinoid
Element 96: Curium (Cm), Actinoid
Element 97: Berkelium (Bk), Actinoid
Element 98: Californium (Cf), Actinoid
Element 99: Einsteinium (Es), Actinoid
Element 100: Fermium (Fm), Actinoid
Element 101: Mendelevium (Md), Actinoid
Element 102: Nobelium (No), Actinoid
Element 103: Lawrencium (Lr), Actinoid
Element 104: Rutherfordium (Rf), Transition metal
Element 105: Dubnium (Db), Transition metal
Element 106: Seaborgium (Sg), Transition metal
Element 107: Bohrium (Bh), Transition metal
Element 108: Hassium (Hs), Transition metal
Element 109: Meitnerium (Mt), Transition metal
Element 110: Darmstadtium (Ds), Transition metal
Element 111: Roentgenium (Rg), Transition metal
Element 112: Ununbium (Uub), Transition metal
Element 113: Ununtrium (Uut), Other metal
Element 114: Ununquadium (Uuq), Other metal
Element 115: Ununpentium (Uup), Other metal
Element 116: Ununhexium (Uuh), Other metal
Element 117: Ununseptium (Uus)
Element 118: Ununoctium (Uuo)
Mercury has a rhombohedral crystal structure
Electron shell for Mercury
80Hg
Periodic table
Appearance
silvery
Pouring liquid mercury bionerd.jpg
General
Name, symbol, number Mercury, Hg, 80
Element category transition metal
Group, period, block 12, 6, d
Standard atomic weight 200.59(2) g·mol−1
Electron configuration [Xe] 4f14 5d10 6s2
Electrons per shell 2, 8, 18, 32, 18, 2 (Image)
Physical properties
Phase liquid
Density (near r.t.) (liquid) 13.534 g·cm−3
Melting point 234.32 K, -38.83 °C, -37.89 °F
Boiling point 629.88 K, 356.73 °C, 674.11 °F
Critical point 1750 K, 172.00 MPa
Heat of fusion 2.29 kJ·mol−1
Heat of vaporization 59.11 kJ·mol−1
Specific heat capacity (25 °C) 27.983 J·mol−1·K−1
Vapor pressure
P/Pa 1 10 100 1 k 10 k 100 k
at T/K 315 350 393 449 523 629
Atomic properties
Oxidation states 4, 2 (mercuric), 1 (mercurous)
(mildly basic oxide)
Electronegativity 2.00 (Pauling scale)
Ionization energies 1st: 1007.1 kJ·mol−1
2nd: 1810 kJ·mol−1
3rd: 3300 kJ·mol−1
Atomic radius 151 pm
Covalent radius 132±5 pm
Van der Waals radius 155 pm
Miscellaneous
Crystal structure rhombohedral
Magnetic ordering diamagnetic
Electrical resistivity (25 °C) 961nΩ·m
Thermal conductivity (300 K) 8.30 W·m−1·K−1
Thermal expansion (25 °C) 60.4 µm·m−1·K−1
Speed of sound (liquid, 20 °C) 1451.4 m/s
CAS registry number 7439-97-6
Most stable isotopes
Main article: Isotopes of Mercury
iso NA half-life DM DE (MeV) DP
194Hg syn 444 y ε 0.040 194Au
195Hg syn 9.9 h ε 1.510 195Au
196Hg 0.15% 196Hg is stable with 116 neutrons
197Hg syn 64.14 h ε 0.600 197Au
198Hg 9.97% 198Hg is stable with 118 neutrons
199Hg 16.87% 199Hg is stable with 119 neutrons
200Hg 23.1% 200Hg is stable with 120 neutrons
201Hg 13.18% 201Hg is stable with 121 neutrons
202Hg 29.86% 202Hg is stable with 122 neutrons
203Hg syn 46.612 d β 0.492 203Tl
204Hg 6.87% 204Hg is stable with 124 neutrons
 

Mercury (pronounced /ˈmɜrkjʊri/), also called quicksilver (/ˈkwɪksɪlvər/) or hydrargyrum (/haɪˈdrɑrdʒɨrəm/), is a chemical element with the symbol Hg (Latinized Greek: hydrargyrum, meaning watery or liquid silver) and atomic number 80. A heavy, silvery d-block metal, mercury is one of six chemical elements that are liquid at or near room temperature and pressure,[1][2] the others being caesium, francium, gallium, bromine, and rubidium. Mercury is the only metal that is liquid at standard conditions for temperature and pressure. With a melting point of −38.83 °C and boiling point of 356.73 °C, mercury has one of the widest ranges of its liquid state of any metal.

Mercury occurs in deposits throughout the world mostly as cinnabar (mercuric sulfide), which is the source of the red pigment vermilion, and is mostly obtained by reduction from cinnabar. Cinnabar is highly toxic by ingestion or inhalation of the dust, and mercury poisoning can also result from exposure to soluble forms (such as mercuric chloride or methylmercury), inhalation of mercury vapor, or eating fish contaminated with mercury.

Mercury is used in thermometers, barometers, manometers, sphygmomanometers, float valves, and other scientific apparatus, though concerns about the element's toxicity have led to mercury thermometers and sphygmomanometers being largely phased out in clinical environments in favor of alcohol-filled, digital, or thermistor-based instruments. It remains in use in a number of other ways in scientific and scientific research applications, and in amalgam material for dental restoration. It is used in lighting; electricity passed through mercury vapor in a phosphor tube produces short-wave ultraviolet light which then causes the phosphor to fluoresce, making visible light.

Contents

Properties

Physical

A pound coin floats in mercury due to the buoyant force upon it.

Mercury is a heavy, silvery-white metal. As compared to other metals, it is a poor conductor of heat, but a fair conductor of electricity. [3] Mercury has an exceptionally low melting temperature for a d-block metal. A complete explanation of this fact requires a deep excurse into quantum physics, but it can be summarized as follows: mercury has a unique electronic configuration where electrons fill up all the available 1s, 2s, 2p, 3s, 3p, 3d, 4s, 4p, 4d, 4f, 5s, 5p, 5d and 6s subshells. As such configuration strongly resists removal of an electron, mercury behaves similarly to noble gas elements, which form weakly bonded and thus easily melting solids. The stability of the 6s shell is due to the presence of a filled 4f shell. An f shell poorly screens the nuclear charge that increases the attractive Coulomb interaction of the 6s shell and the nucleus (see lanthanide contraction). The absence of a filled inner f shell is the reason for much higher melting temperature of cadmium. Metals such as gold have atoms with one less 6s electron than mercury. Those electrons are more easily removed and are shared between the gold atoms forming relatively strong metallic bonds. [2][4]

Reactivity and compounds

Mercury dissolves to form amalgams with gold, zinc and many other metals. Because iron is an exception, iron flasks have been traditionally used to trade mercury. Other metals that do not form amalgams with mercury include tantalum, tungsten and platinum. When heated, mercury also reacts with oxygen in air to form mercury oxide, which then can be decomposed by further heating to higher temperatures.[5]

Since it is below hydrogen in the reactivity series of metals, mercury does not react with most acids, such as dilute sulfuric acid, though oxidizing acids such as concentrated sulfuric acid and nitric acid or aqua regia dissolve it to give sulfate, nitrate, and chloride salts. Like silver, mercury reacts with atmospheric hydrogen sulfide. Mercury even reacts with solid sulfur flakes, which are used in mercury spill kits to absorb mercury vapors (spill kits also use activated charcoal and powdered zinc).[5]

Some important mercury salts include:

  • Mercury(I) chloride (calomel) is sometimes still used in medicine, acousto-optical filters and as a standard in electrochemistry;[6]
  • Mercury(II) chloride is a very corrosive, easily sublimating and poisonous substance;[3]
  • Mercury fulminate, (a detonator widely used in explosives);[3]
  • Mercury(II) oxide, the main oxide of mercury;
  • Mercury(II) sulfide (found naturally as the ore cinnabar, or vermilion which is a high-grade paint pigment);[3]
  • Mercury(II) selenide, Mercury(II) telluride, Mercury cadmium telluride and mercury zinc telluride are semiconductors and infrared detector materials.[7]

In these compounds, mercury displays two oxidation states: +1 and +2. The +1 state oxidation involves the dimeric cation, Hg2+2. Solutions of Hg2+2 are in equilibrium with Hg2+ and metallic mercury:

Hg2+ + Hg is in equilibrium with Hg2+2

This equilibrium causes solutions of Hg2+2 to have a small amount of Hg2+ present. Consuming the Hg2+ by another reaction, such as complexation with strong ligands or precipitation of an insoluble salt, will cause all the Hg2+2 to fully disproportionate to Hg2+ and elemental mercury.[8]

Higher oxidation states of mercury were confirmed in September 2007, with the synthesis of mercury(IV) fluoride (HgF4) using matrix isolation techniques.[9]

Laboratory tests have found that an electrical discharge causes the noble gases to combine with mercury vapor. These compounds are held together with van der Waals forces and result in Hg·Ne, Hg·Ar, Hg·Kr, and Hg·Xe (see exciplex). Organic mercury compounds are also important. Methylmercury is a dangerous compound that is widely found as a pollutant in water bodies and streams.[10]

Mercury and aluminium

Mercury readily combines with aluminium to form a mercury-aluminium amalgam when the two pure metals come into contact. However, when the amalgam is exposed to air, the aluminium oxidizes, leaving mercury behind. The oxide flakes away, exposing more mercury amalgam, which repeats the process. This process continues until the supply of amalgam is exhausted. Because this process releases mercury, a small amount of mercury can "eat through" a large amount of aluminium over time, by progressively forming amalgam and relinquishing the aluminium as oxide.[11]

Aluminium in air is ordinarily protected by a molecule-thin layer of its own oxide, which is not porous to oxygen. Mercury coming into contact with this oxide does no harm. However, if any elemental aluminium is exposed (even by a recent scratch), the mercury may combine with it, starting the process described above, and potentially damaging a large part of the aluminium before it finally ends.[11][12] For this reason, restrictions are placed on the use and handling of mercury in proximity with aluminium. In particular, mercury is not allowed aboard aircraft under most circumstances because of the risk of it forming an amalgam with exposed aluminium parts in the aircraft.[11]

Isotopes

There are seven stable isotopes of mercury with 202Hg being the most abundant (29.86%). The longest-lived radioisotopes are 194Hg with a half-life of 444 years, and 203Hg with a half-life of 46.612 days. Most of the remaining radioisotopes have half-lives that are less than a day. 199Hg and 201Hg are the most often studied NMR-active nuclei, having spins of 12 and 32 respectively.[3]

History

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

Mercury was known to the ancient Chinese[13] and was found in Egyptian tombs that date from 1500 BCE.[14] In China and Tibet, mercury use was thought to prolong life, heal fractures, and maintain generally good health. One of China's emperors, 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 killed by drinking a mercury and powdered jade mixture (causing liver failure, poisoning, and brain death) intended to give him eternal life.[15][16] The ancient Greeks used mercury in ointments; the ancient Egyptians and the Romans used it in cosmetics which sometimes deformed the face. By 500 BC mercury was used to make amalgams with other metals.[17] The Indian word for alchemy is Rasavātam which means "the way of mercury".[18]

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 was the goal of many alchemists.[19]

Hg is the modern chemical symbol for mercury. It comes from hydrargyrum, a Latinized form of the Greek word Ύδραργυρος (hydrargyros), which is a compound word meaning "water" and "silver" — since it is liquid, like water, and yet has a silvery metallic sheen. The element was named after the Roman god Mercury, known for speed and mobility. It is associated with the planet Mercury; the astrological symbol for the planet is also one of the alchemical symbols for the metal. Mercury is the only metal for which the alchemical planetary name became the common name.[19]

The mines in Almadén (Spain), Monte Amiata (Italy), and Idrija (now Slovenia) dominated the 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.[20]

Occurrence

Mercury output in 2005

Mercury is an extremely rare element in the Earth's crust, having an average crustal abundance by mass of only 0.08 parts per million (ppm).[21] However, 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, corderoite, livingstonite and other minerals, with cinnabar (HgS) being the most common ore. Mercury ores usually occur in very young orogenic belts where rock of high density are forced to the crust of the Earth, often in hot springs or other volcanic regions.[22]

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 Almaden in Southern Spain supplied all the mercury for the colonies.[23] 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. The patio process and later pan amalgamation process continued to create great demand for mercury to treat silver ores until the late 1800s.[24]

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.[25]

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

In 2005, China was the top producer of mercury with almost two-thirds global share followed by Kyrgyzstan.[26] Several other countries are believed to have unrecorded production of mercury from copper electrowinning processes and by recovery from effluents.

Because of the high toxicity of mercury, both the mining of cinnabar and refining for mercury are hazardous and historic causes of mercury poisoning. In China, prison labor was used by a private mining company as recently as the 1950s to create new cinnabar mercury mines. Thousands of prisoners were used by the Luo Xi mining company to establish new tunnels.[27] In addition, worker health in functioning mines is at high risk.

The European Union directive calling for compact fluorescent bulbs to be made mandatory by 2012 has encouraged China to re-open deadly cinnabar mines to obtain the mercury required for CFL bulb manufacture. As a result, new generations of Chinese, their livestock, and their crops are being poisoned, particularly in the southern cities of Foshan and Guangzhou, and in the Guizhou province in the southwest.[27]

Abandoned mercury mine processing sites often contain very hazardous waste piles of roasted cinnabar calcines. Water runoff 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.[28]

Releases in the environment

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 in the range of 4 ng /(1 L of ice deposit). Although that can be considered a natural level of exposure, regional or global sources have significant effects. Volcanic eruptions can increase the atmospheric source by 4 — 6 times.[29]

Natural sources such as volcanoes are responsible for approximately half of atmospheric mercury emissions. The human-generated half can be divided into the following estimated percentages:[30][31][32]

  • 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.[30]
  • 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.[33]
  • 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. This is a significant underestimate due to limited information, and is likely to be off by a factor of two to five.
  • 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.[30]

Current atmospheric mercury contamination in outdoor urban air is (0.01 – 0.02 µg/m3 ) indoor concentrations are significantly elevated over outdoor concentrations, at a range of 0.0065 – 0.523 µg/m3 (average 0.069 µg/m3) [34]

Mercury also enters into the environment through the disposal (e.g., land filling, incineration) of certain products. Products containing mercury include: auto parts, batteries, fluorescent bulbs, medical products, thermometers, and thermostats.[35] Due to health concerns (see below), toxics use reduction efforts are cutting back or eliminating mercury in such products. For example, most thermometers now use pigmented alcohol instead of mercury. Mercury thermometers are still occasionally used in the medical field because they are more accurate than alcohol thermometers, though both are being replaced by electronic thermometers. Mercury thermometers are still widely used for certain scientific applications because of their greater accuracy and working range.

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 EPA rule[36] added power plants to the list of sources that should be controlled and a national cap and trade rule was issued. States were given until November 2006 to impose stricter controls, and several States are doing so. The rule was being subjected to legal challenges from several States in 2005 and decision was made in 2008. The Clean Air Mercury Rule was struck down by a Federal Appeals Court on February 8, 2008. The rule was deemed not sufficient to protect the health of persons living near coal-fired power plants. The court opinion cited the negative impact on human health from coal fired power plants' mercury emissions documented in the EPA Study Report to Congress of 1998.[37]

Historically, one of the largest releases was from the Colex plant, a lithium-isotope separation plant at Oak Ridge. The plant operated in the 1950s and 1960s. Records are incomplete and unclear, but government commissions have estimated that some two million pounds of mercury are unaccounted for.[38]

One of the worst industrial disasters in history was caused by the dumping of mercury compounds into Minamata Bay, Japan. The Chisso Corporation, a fertilizer and later petrochemical company, was found responsible for polluting the bay from 1932 — 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.[39]

Applications

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 thermometers, especially ones which are 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 phased out due to health and safety regulations and is in some applications replaced with less toxic but considerably more expensive Galinstan alloy.

Present use

Medicine

Amalgam filling
The deep violet glow of a mercury vapor discharge in a germicidal lamp, whose spectrum is rich in invisible ultraviolet radiation.

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. The element mercury is an ingredient in dental amalgams. Thiomersal (called Thimerosal in the United States) is an organic compound used as a preservative in vaccines, though this use is in decline.[40] Another mercury compound Merbromin (Mercurochrome) is a topical antiseptic used for minor cuts and scrapes is still in use in some countries.

Mercury(I) chloride (also known as calomel or mercurous chloride) has traditionally been used 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.[41] It was also used as a disinfectant. Blue mass, a pill or syrup in which mercury is the main ingredient, was prescribed throughout the 1800s for numerous conditions including constipation, depression, child-bearing and toothaches.[42] 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.[43]

Since the 1930s some vaccines have contained the preservative thiomersal, which is metabolized or degraded to ethyl mercury. Although it was widely speculated that this mercury-based preservative can cause or trigger autism in children, scientific studies showed no evidence supporting any such link.[44] 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 inactivated influenza vaccine.[45]

Mercury in the form of one of its common ores, cinnabar, remains an important component of Chinese, Tibetan, and Ayurvedic medicine. As problems may arise when these medicines are exported to countries that prohibit the use of mercury in medicines, in recent times, less toxic substitutes have been devised.

Today, the use of mercury in medicine has greatly declined in all respects, especially in developed countries. Thermometers and sphygmomanometers containing mercury were invented in the early 18th and late 19th centuries, respectively. In the early 21st century, their use is declining and has been banned in some countries, states and medical institutions. In 2002, the U.S. Senate passed legislation to phase out the sale of non-prescription mercury thermometers. In 2003, Washington and Maine became the first states to ban mercury blood pressure devices.[46] Mercury compounds are 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.[47] Mercury is still used in some diuretics, although substitutes now exist for most therapeutic uses.

Cosmetics

Mercury, as thiomersal, is widely used in the manufacture of mascara. In 2008, Minnesota became the first state in the US to ban intentionally added mercury in cosmetics, giving it a tougher standard than the federal government.[48]

Production of chlorine and caustic soda

Chlorine is produced from sodium chloride (common salt, NaCl) using electrolysis to separate the metallic sodium from the chlorine gas. Usually the 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[49][50] in the late 1900s 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.[51] Many of the industrial mercury releases of the 1900s came from this process, although modern plants claimed to be safe in this regard.[50] After about 1985, all new chloralkali production facilities that were built in the United States used either membrane cell or diaphragm cell technologies to produce chlorine.

Gold and silver mining

Historically, mercury was used extensively in hydraulic gold mining in order to help the gold to sink through the flowing water-gravel mixture. Thin mercury particles may form mercury-gold amalgam and therefore increase the gold recovery rates.[3] Large scale use of mercury stopped in the 1960s. However, mercury is still used in small scale, often clandestine, gold prospection. It is estimated that 45,000 metric tons of mercury used in California for placer mining have not been recovered.[52] Mercury was also used in silver mining.[53]

Other present uses

Skin tanner containing a low-pressure mercury vapor lamp and two infrared lamps, which act both as light source and electrical ballast
Assorted types of fluorescent lamps.

Gaseous mercury is used in mercury-vapor lamps and some "neon sign" type advertising signs and fluorescent lamps. 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; however simply reflecting some of the fluorescent-lamp ceiling light into a spectrometer is a common calibration practice.[54] Gaseous mercury is also found in some electron tubes, including ignitrons, thyratrons, and mercury arc rectifiers.[55] It is also used in specialty medical care lamps for skin tanning and desinfection (see pictures).[56] 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 the light produced will be inconsistent red/blue spots until the initial burning-in process is completed; eventually it will light a consistent dull off-blue color.[57]

Some medical thermometers, especially those for high temperatures, are filled with mercury, however, they are gradually disappearing. In the United States, non-prescription sale of mercury fever thermometers has been banned in 2003. [58] It is also found in liquid-mirror telescopes. The mirror is formed by rotating liquid mercury on a disk, the parabolic form of the liquid thus formed reflecting and focusing incident light. Such 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.[59][60]

Liquid mercury is a part of 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.[61] Last, but not least, the triple point of mercury, -38.8344 °C, is a fixed point used as a temperature standard for the International Temperature Scale (ITS-90).[3]

Proposed uses

Liquid mercury has been proposed as a working fluid for a heat pipe type of cooling device for spacecraft heat rejection systems or radiation panels.[62] A new type of atomic clock, using mercury instead of caesium, has been demonstrated. Accuracy is expected to be within one second in 100 million years.[63][64]

Historic uses

Old mercury switches
Mercury manometer to measure pressure

Mercury was used for preserving wood, developing daguerreotypes, silvering mirrors, anti-fouling paints (discontinued in 1990), herbicides (discontinued in 1995), handheld maze games, cleaning, and road leveling devices in cars. Mercury compounds have been used in antiseptics, laxatives, antidepressants, and in antisyphilitics. It was also allegedly used by allied spies to sabotage German planes. A mercury paste was applied to bare aluminium, causing the metal to rapidly corrode. This would cause structural failures.[12]

  • Mercury switches (including home mercury light switches installed prior to 1970), tilt switches used in old fire detectors, tilt switches in many modern home thermostats,[65] electrodes in some types of electrolysis, batteries (mercury cells), sodium hydroxide and chlorine production, handheld games, catalysts, insecticides and liquid mirror telescopes.[66]
  • 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.[67]
  • Mercury was used inside wobbler lures. Its heavy, liquid form made it useful since the lures made an attractive irregular movement when the mercury moved inside the plug. Such use was stopped due to environmental concerns, but illegal preparation of modern fishing plugs has occurred.
  • The Fresnel lenses of old lighthouses used to float and rotate in a bath of mercury which acted like a bearing.[68]
  • Mercury sphygmomanometers (blood pressure meter), barometers, diffusion pumps, coulometers, and many other laboratory instruments. As an opaque liquid with a high density and a nearly linear thermal expansion, it is ideal for this role.[69]
  • 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.[70]
  • Mercury was a propellant for early ion engines in electric 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 SERT-1 launched by NASA at its Wallops Flight Facility in 1964. SERT stands for Space Electric Rocket Test. 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 its noble gas nature, and has a high liquid density under mild cryogenic storage.[71][72]
  • Experimental mercury vapor turbines were installed to increase the efficiency of fossil-fuel electrical power plants.[73]
  • Mercury was once used as a gun barrel bore cleaner.[74][75]

Hat making

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)2·2H2O.[76] 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 are said by some to have inspired the phrase "mad as a hatter", though etymological study suggests that the phrase is actually much older and unrelated to hatters - see hatter for commentary on the origin of the phrase. 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.[77]

Safety

Mercury and most of its compounds are extremely toxic and are generally handled with care; in cases of spills involving mercury (such as from certain thermometers or fluorescent light bulbs) specific cleaning procedures are used to avoid toxic exposure.[78] It can be inhaled and absorbed through the skin and mucous membranes, so containers of mercury are securely sealed to avoid spills and evaporation. Heating of mercury, or compounds of mercury that may decompose when heated, are always carried out with adequate ventilation in order to avoid exposure to mercury vapor. The most toxic forms of mercury are its organic compounds, such as dimethylmercury and methylmercury. However, inorganic compounds, such as cinnabar are also highly toxic by ingestion or inhalation of the dust.[79] Mercury can cause both chronic and acute poisoning.

Occupational exposure

Due to the health effects of mercury exposure, industrial and commercial uses are regulated in many countries. The World Health Organization, OSHA, and NIOSH all treat mercury as an occupational hazard, and have established specific occupational exposure limits. Environmental releases and disposal of mercury are regulated in the U.S. primarily by the United States Environmental Protection Agency.

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.[80][81] 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.[82] 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.[83][84]

Treatment

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.[85] 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.[86]

Fish

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, albacore tuna, and tilefish contain higher concentrations of mercury than others. As mercury and methylmercury are fat soluble, they primarily accumulate in the viscera, although they are also found throughout the muscle tissue. When this fish is consumed by a predator, the mercury level is accumulated. Since fish are less efficient at depurating than accumulating methylmercury, fish-tissue concentrations 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. As a result, those consuming high levels of fish should be aware of the symptoms of mercury poisoning. [87]

Regulations

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.[88] North America contributed approximately 11% of the total global anthropogenic mercury emissions in 1995.[89]

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.[90] There are restriction 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).[91] 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. [92]

Norway enacted a total ban on the use of mercury in the manufacturing and import/export of mercury products, effective January 1, 2008.[93] In 2002, several lakes in Norway were found to have a poor state of mercury pollution, with an excess of 1 mg/g of mercury in their sediment.[94]

References

Further reading

  • Jane M. Hightower Diagnosis: Mercury: Money, Politics, and Poison Island Press (October 1, 2008) ISBN 1597263958 ISBN 978-1597263955

External links