Heavy metal (chemistry)

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"heavy metal poisoning" redirects here. For the 1983 Styx song, see Heavy Metal Poisoning.
A 25-foot (7.6 m) wall of heavy metal contaminated coal fly ash, resulting from the release of 5.4 million cubic yards of coal fly ash slurry into the Emory River, Tennessee, and nearby land and water features, in December 2008.[1] Testing showed significantly elevated levels of arsenic, copper, barium, cadmium, chromium, lead, mercury, nickel, and thallium in samples of slurry and river water.[2] Cleanup costs may exceed $1.2 billion.[3]

A heavy metal is any metal or metalloid of environmental concern. The term originated with reference to the harmful effects of cadmium, mercury and lead, all of which are denser than iron. It has since been applied to any other similarly toxic metal, or metalloid such as arsenic,[4] regardless of density.[5] Commonly encountered heavy metals are chromium, cobalt, nickel, copper, zinc, arsenic, selenium, silver, cadmium, antimony, mercury, thallium and lead. More specific definitions of a heavy metal have been proposed; none have obtained widespread acceptance.[6]

Definitions[edit]

Criteria used to define heavy metals have included density, atomic weight, atomic number, or periodic table position.[7] Density criteria range from above 3.5 g/cm3 to above 7 g/cm3. Atomic weight definitions start at greater than sodium (22.98) to greater than 40.[n 1] Atomic numbers of heavy metals are generally given as greater than 20; sometimes this is capped at 92 (uranium). Hawkes suggested referring to heavy metals as "all the metals in Groups 3 to 16 that are in periods 4 and greater."[9] There is no widely agreed definition of a heavy metal.

The term "heavy metals" was in use as far back as 1817, when Gmelin divided the elements into nonmetals, light metals and heavy metals.[10] Light metals had densities of 0.860–5.0 gm/cm3; heavy metals 5.308–22.000.[11] In 1868, Wanklyn and Chapman speculated on the adverse effects of the heavy metals "arsenic, lead, copper, zinc, iron and manganese" in drinking water. They noted an "absence of investigation" and were reduced to "the necessity of pleading for the collection of data."[12] In 1884, Blake described a connection between toxicity and the atomic weight of an element.[13]

Beryllium and aluminium, although light metals, are sometimes counted as heavy metals in view of their toxicity.[14][15] Beryllium exposure can result in lung and heart disorders, and possibly death;[16] aluminium is a major inhibitor of crop growth in acid soils.[17]

Contamination sources[edit]

Tetraethyl lead (CH3CH2)4Pb is probably the most significant heavy metal contaminant in recent use.[18]

Heavy metals are found naturally in the earth, and become concentrated as a result of human caused activities. Common sources are from mining and industrial wastes; vehicle emissions; lead-acid batteries; fertilisers, paints and treated woods. Lead is the most prevalent heavy metal contaminant.[19] As a component of tetra-ethyl lead it was used extensively in gasoline during the 1930s-1970s.[20] Lead levels in the aquatic environments of industrialised societies have been estimated to be two to three times those of pre-industrial levels.[21] Although the use of leaded gasoline was largely phased out in North America by 1996, soils next to roads built before this time retain high concentrations of lead.

Entry routes[edit]

Heavy metals enter plant, animal and human tissues via air inhalation, diet and manual handling. Motor vehicle emissions are a major source of airborne contaminants including arsenic, cadmium, cobalt, nickel, lead, antimony, vanadium, zinc, platinum, palladium and rhodium.[22] Water sources (groundwater, lakes, streams and rivers) can be polluted by heavy metals leaching from industrial and consumer waste; acid rain can exacerbate this process by releasing heavy metals trapped in soils.[23] Plants are exposed to heavy metals through the uptake of water; animals eat these plants; ingestion of plant- and animal-based foods are the largest sources of heavy metals in humans.[24] Absorption through skin contact, for example from contact with soil, is another potential source of heavy metal contamination.[25] Heavy metals can accumulate in organisms as they are hard to metabolize (process and eliminate).[26]

Detrimental effects[edit]

Heavy metals "can bind to vital cellular components, such as structural proteins, enzymes, and nucleic acids, and interfere with their functioning."[27] Symptoms and effects can vary according to the metal or metal-compound, and the dose involved. Broadly, long-term exposure to heavy metals can have carcinogenic, central and peripheral nervous system and circulatory effects. For humans, typical presentations associated with exposure to the "classical"[28] heavy metals; chromium (another heavy metal); and arsenic (a metalloid), are shown in the table.[29]

Element Acute exposure Chronic exposure Main article
Cadmium Pneumonitis (lung inflammation) Lung cancer
Osteomalacia (softening of bones)
Proteinuria (excess protein in urine; possible kidney damage) 
Cadmium poisoning 
Mercury Diarrhea
Fever
Vomiting
Stomatitis (inflammation of gums and mouth)
Nausea
Nephrotic syndrome (nonspecific kidney disorder)
Neurasthenia (neurotic disorder)
Parageusia (metallic taste)
Pink Disease (pain and pink discoloration of hands and feet)
Tremor
Mercury poisoning
Lead Encephalopathy (brain dysfunction)
Nausea
Vomiting
Anemia
Encephalopathy
Foot drop/wrist drop (palsy)
Nephropathy (kidney disease)
Lead poisoning
Chromium  Gastrointestinal hemorrhage (bleeding) 
Hemolysis (red blood cell destruction)
Acute renal failure
Pulmonary fibrosis (lung scarring)
Lung cancer
Chromium toxicity
Arsenic Nausea
Vomiting
Diarrhea
Encephalopathy
Multi-organ effects
Arrhythmia
Painful neuropathy
Diabetes
Hypopigmentation/Hyperkeratosis
Cancer
Arsenic poisoning

Historical reports (examples)[edit]

99.999% purity cadmium bar and 1 cm3 cube.

Cadmium[edit]

Cadmium exposure is a phenomenon of the early 20th century, and onwards. In Japan in 1910, the Mitsui Mining and Smelting Company began discharging cadmium into the Jinzugawa river, as a byproduct of mining operations. Residents in the surrounding area subsequently consumed rice grown in cadmium contaminated irrigation water. They experienced softening of the bones and kidney failure. The origin of these symptoms was not clear; possibilities raised at the time included "a regional or bacterial disease or lead poisoning."[30] In 1955, cadmium was identified as the likely cause and in 1961 the source was directly linked to mining operations in the area.[31] In February 2010, cadmium was found in Wal-Mart exclusive Miley Cyrus jewelry. Wal-Mart continued to sell the jewelry until May, when covert testing organised by Associated Press confirmed the original results.[32] In June 2010 cadmium was detected in the paint used on promotional drinking glasses for the movie Shrek Forever After, sold by McDonald's Restaurants, triggering a recall of 12 million glasses.[33]

Saint Isaac's Cathedral, in Saint Petersburg, Russia. The gold-mercury amalgam used to gild its dome caused numerous casualties among the workers involved.

Mercury[edit]

The first emperor of unified China, Qin Shi Huang, it is reported, died of ingesting mercury pills that were intended to give him eternal life.[34] The phrase "mad as a hatter" is likely a reference to mercury poisoning among milliners (so-called "mad hatter disease"), as mercury-based compounds were once used in the manufacture of felt hats in the 18th and 19th century.[35] Historically, gold amalgam (an alloy with mercury) was widely used in gilding, leading to numerous casualties among the workers. It is estimated that during the construction of Saint Isaac's Cathedral alone, 60 workers died from the gilding of the main dome.[36] Outbreaks of methylmercury poisoning occurred in several places in Japan during the 1950s due to industrial discharges of mercury into rivers and coastal waters. The best-known instances were in Minamata and Niigata. In Minamata alone, more than 600 people died due to what became known as Minamata disease. More than 21,000 people filed claims with the Japanese government, of which almost 3000 became certified as having the disease. In 22 documented cases, pregnant women who consumed contaminated fish showed mild or no symptoms but gave birth to infants with severe developmental disabilities.[37] Since the industrial Revolution, mercury levels have tripled in many near-surface seawaters, especially around Iceland and Antarctica.[38]

Lead[edit]

The adverse effects of lead were known to the ancients. In the 2nd century BC the Greek botanist Nicander described the colic and paralysis seen in lead-poisoned people.[39] Dioscorides, a Greek physician who is thought to have lived in the 1st century CE,[40] wrote that lead "makes the mind give way". Lead was used extensively in Roman aqueducts from about 500 BC to 300 AD.[41] Julius Caesar's engineer, Vitruvius, reported, "water is much more wholesome from earthenware pipes than from lead pipes. For it seems to be made injurious by lead, because white lead is produced by it, and this is said to be harmful to the human body."[42] In 2013, the World Health Organization estimated that lead poisoning resulted in 143,000 deaths, and "contribute[d] to 600,000 new cases of children with intellectual disabilities", each year.[43]

Potassium chromate, a carcinogen, is used in the dyeing of fabrics, and as a tanning agent to produce leather.

Chromium[edit]

Chromium(III) compounds and chromium metal are not considered a health hazard, while the toxicity and carcinogenic properties of chromium(VI) have been known since at least the late 19th century.[44] In 1890, Newman described the elevated cancer risk of workers in a chromate dye company.[45] Chromate-induced dermatitis was reported in aircraft workers during World War II.[46] In 1963, an outbreak of dermatitis, ranging from erythema to exudative eczema, occurred amongst 60 automobile factory workers in England. The workers had been wet-sanding chromate-based primer paint that had been applied to car bodies.[47] In Australia, chromium was released from the Newcastle Orica explosives plant on August 8, 2011. Up to 20 workers at the plant were exposed as were 70 nearby homes in Stockton. The town was only notified three days after the release and the accident sparked a major public controversy, with Orica criticised for playing down the extent and possible risks of the leak, and the state Government attacked for their slow response to the incident.[48]

Arsenic[edit]

Orpiment, a toxic arsenic mineral used in the tanning industry to remove hair from hides.

Arsenic, as realgar (As4S4) and orpiment (As2S3), was known in ancient times. Strabo (64–50 BCE – c. AD 24?), a Greek geographer and historian,[49] wrote that only slaves were employed in realgar and orpiment mines since they would inevitably die from the toxic effects of the fumes given off from the ores. Arsenic contaminated beer poisoned over 6,000 people in the Manchester area of England in 1900, and is thought to have killed at least 70 victims.[50] Clare Luce, American ambassador to Italy from 1953 to 1956, suffered from arsenic poisoning. Its source was traced to flaking arsenic-laden paint on the ceiling of her bedroom. She may also have eaten food contaminated by arsenic in flaking ceiling paint in the embassy dining room.[51] Ground water contaminated by arsenic, as at 2014, "is still poisoning millions of people in Asia."[52]

Remediation[edit]

A metal EDTA anion. Pb displaces Ca in Na2[CaEDTA] to give Na2[PbEDTA], which is passed out of the body in urine.[53]

In humans, heavy metal poisoning is generally treated by the administration of chelating agents.[54] These are chemical compounds, such as CaNa2 EDTA (calcium disodium ethylenediaminetetraacetate) that convert heavy metals to chemically inert forms that can be excreted without further interaction with the body. Chelates are not without side effects and can also remove beneficial metals from the body. Vitamin and mineral supplements are sometimes co-administered for this reason.[55]

Soils contaminated by heavy metals can be re-mediated by one or more of the following technologies: isolation; immobilization; toxicity reduction; physical separation; or extraction. Isolation involves the use of caps, membranes or below-ground barriers in an attempt to quarantine the contaminated soil. Immobilization aims to alter the properties of the soil so as to hinder the mobility of the heavy contaminants. Toxicity reduction attempts to oxidise or reduce the heavy metal ions, via chemical or biological means into less toxic or mobile forms. Physical separation involves the removal of the contaminated soil and the separation of the metal contaminants by mechanical means. Extraction is an on or off-site process that uses chemicals, high-temperature volatization, or electrolysis to extract contaminants from soils. The process or processes used will vary according to contaminant and the characteristics of the site.[56]

Benefits[edit]

Some elements regarded as heavy metals are essential, in small quantities, for human health. These elements include vanadium, manganese, iron, cobalt, copper, zinc, selenium, strontium and molybdenum.[57] A deficiency of these essential metals may increase susceptibility to heavy metal poisoning.[58]

See also[edit]

Notes[edit]

  1. ^ Excluding s- and f-block metals, hence starting with scandium[8]

Citations[edit]

  1. ^ Dewan 2008
  2. ^ Dewan 2009
  3. ^ Poovey 2001
  4. ^ Kumar, Abbas & Aster 2013, p. 276
  5. ^ Duffus 2002; Newman & Unger 2003, pp. 21–2
  6. ^ Sengupta 2002, pp. 1–2
  7. ^ Duffus 2002
  8. ^ Rand 1995, p. 23
  9. ^ Hawkes 1997
  10. ^ Habashi 2009, p. 31
  11. ^ Gmelin 1849, p. 2
  12. ^ Wanklyn & Chapman 1868, pp. 73–8; Cameron 1871, p. 484
  13. ^ Blake 1884
  14. ^ Volesky 1990, pp. 14–15
  15. ^ Park 2013, p. 87;Blann & Ahmed 2014, p. 465
  16. ^ Cooper & Harrison 2009
  17. ^ Saxena & Misra 2010, pp. 436–7
  18. ^ Wright 2002, p. 288
  19. ^ Di Maio 2001, p. 527
  20. ^ Lovei 1998, p. 15
  21. ^ Perry & Vanderklein 1996, p. 336
  22. ^ Balasubramanian, He & Wang 2009, p. 476
  23. ^ Worsztynowicz & Mill 1995, p. 361
  24. ^ Radojevic & Bashkin 1999, p. 406
  25. ^ Qu et al. 2014, p. 144
  26. ^ Pezzarossa, Gorini & Petruzelli 2011, p. 94
  27. ^ Lanids, Sofield & Yu 2000, p. 269
  28. ^ Neilen & Marvin 2008, p. 10
  29. ^ Afal & Wiener 2014
  30. ^ Vallero & Letcher 2013, p. 240
  31. ^ Vallero & Letcher 2013, pp. 239–241
  32. ^ Pritchard 2010
  33. ^ Mulvihill & Pritchard 2010
  34. ^ Zhao, Zhu & Sui 2006
  35. ^ Waldron 1983
  36. ^ Emsely 2011, p. 326
  37. ^ Davidson, Myers & Weiss 2004, p. 1025
  38. ^ New Scientist 2014, p. 4
  39. ^ Pearce 2007; Needleman 2004
  40. ^ Rogers 2000, p. 41
  41. ^ Gilbert & Weiss 2006
  42. ^ Prioreschi 1998, p. 279
  43. ^ World Health Organization 2013
  44. ^ Barceloux & Barceloux 1999
  45. ^ Newman 1890
  46. ^ Haines & Nieboer 1988, p. 504
  47. ^ National Research Council 1974, p. 68
  48. ^ Tovey 2011; Jones 2011; O'Brien & Aston
  49. ^ Dueck 2000, pp. 1–3, 46, 53
  50. ^ Dyer 2009
  51. ^ Whorton 2011, p. 356
  52. ^ Notman 2014
  53. ^ Cs uros 1997, p. 124
  54. ^ Blann & Ahmed 2014, p. 465
  55. ^ American Cancer Society 2008; National Capital Poison Center 2010
  56. ^ Evanko & Dzombak 1997, pp. 1, 14–40
  57. ^ Bánfalvi 2011, p. 12
  58. ^ Chowdhury 1987

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