Chemistry:Toxic heavy metal

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Short description: Category of substances
A 25-foot (7.6 m) wall of coal fly ash contaminated with toxic heavy metals, 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 toxic heavy metal is any relatively dense metal or metalloid that is noted for its potential toxicity, especially in environmental contexts.[4][5] The term has particular application to cadmium, mercury and lead,[6] all of which appear in the World Health Organization's list of 10 chemicals of major public concern. Other examples include manganese, chromium, cobalt, nickel, copper, zinc, silver, antimony and thallium.[7]

Heavy metals are found naturally in the earth. They become concentrated as a result of human caused activities and can enter plant and animal (including human) tissues via inhalation, diet, and manual handling. Then, they can bind to and interfere with the functioning of vital cellular components. The toxic effects of arsenic, mercury, and lead were known to the ancients, but methodical studies of the toxicity of some heavy metals appear to date from only 1868. In humans, heavy metal poisoning is generally treated by the administration of chelating agents. Some elements otherwise regarded as toxic heavy metals are essential, in small quantities, for human health.

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
Examples of toxic heavy metals

Contamination sources

Tetraethyl lead is one of the most significant heavy metal contaminants in recent use.[8]

Heavy metals are found naturally in the earth, and become concentrated as a result of human activities, or, in some cases geochemical processes, such as accumulation in peat soils that are then released when drained for agriculture.[9] Common sources are mining and industrial wastes; vehicle emissions; motor oil; fuels used by ships and heavy machineries; construction works; fertilisers;[10] pesticides; paints; dyes and pigments; renovation; illegal depositing of construction and demolition waste; open top roll-off dumpster; welding, brazing and soldering; glassworking;[11] concrete works; roadworks; use of recycled materials; DIY metal projects; burning of joss paper; open burning of waste in rural area; contaminated ventilation system; food contaminated by the environment or by the packaging; armaments; lead-acid batteries; electronic waste recycling yard; treated woods; aging water supply infrastructure;[12] and microplastics floating in the world's oceans.[13] Arsenic, cadmium and lead may be present in children's toys at levels that exceed regulatory standards. Lead can be used in toys as a stabilizer, color enhancer, or anti-corrosive agent. Cadmium is sometimes employed as a stabilizer, or to increase the mass and luster of toy jewelry. Arsenic is thought to be used in connection with coloring dyes.[14] Regular imbibers of illegally distilled alcohol may be exposed to arsenic or lead poisoning the source of which is arsenic-contaminated lead used to solder the distilling apparatus. Rat poison used in grain and mash stores may be another source of the arsenic.[15]

Lead is the most prevalent heavy metal contaminant.[16] As a component of tetraethyl lead, (CH3CH2)4Pb, it was used extensively in gasoline during the 1930s–1970s.[17] Lead levels in the aquatic environments of industrialised societies have been estimated to be two to three times those of pre-industrial levels.[18] 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 lead concentrations. Lead (from lead(II) azide or lead styphnate used in firearms) gradually accumulates at firearms training grounds, contaminating the local environment and exposing range employees to a risk of lead poisoning.[19]

Entry routes

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.[20] 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.[21] Transport through soil can be facilitated by the presence of preferential flow paths (macropores) and dissolved organic compounds.[22] 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.[23] Absorption through skin contact, for example from contact with soil, or metal containing toys and jewelry,[24] is another potential source of heavy metal contamination.[25] Toxic heavy metals can bioaccumulate in organisms as they are hard to metabolize.[26]

Detrimental effects

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 toxic heavy metals can have carcinogenic, central and peripheral nervous system, and circulatory effects. For humans, typical presentations associated with exposure to any of the "classical"[28] toxic heavy metals, or chromium (another toxic heavy metal) or arsenic (a metalloid), are shown in the table.[29]

Element Acute exposure
usually a day or less 		Chronic exposure
often months or years
Cadmium Pneumonitis (lung inflammation) Lung cancer
Osteomalacia (softening of bones)
Proteinuria (excess protein in urine; possible kidney damage)
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
Lead Encephalopathy (brain dysfunction)
Nausea
Vomiting		 Anemia
Encephalopathy
Foot drop/wrist drop (palsy)
Nephropathy (kidney disease)
Chromium Gastrointestinal hemorrhage (bleeding) 
Hemolysis (red blood cell destruction)
Acute renal failure		 Pulmonary fibrosis (lung scarring)
Lung cancer
Arsenic Nausea
Vomiting
Diarrhea
Encephalopathy
Multi-organ effects
Arrhythmia
Painful neuropathy		 Diabetes
Hypopigmentation/Hyperkeratosis
Cancer

History

The toxic effects of arsenic, mercury and lead were known to the ancients but methodical studies of the overall toxicity of heavy metals appear to date from only 1868. In that year, 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".[30] In 1884, Blake described an apparent connection between toxicity and the atomic weight of an element.[31] The following sections provide historical thumbnails for the "classical" toxic heavy metals (arsenic, mercury and lead) and some more recent examples (chromium and cadmium).

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

Arsenic

Arsenic, as realgar (As4S4) and orpiment (As2S3), was known in ancient times. Strabo (64–50 BCE – c. AD 24?), a Greek geographer and historian,[32] 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.[33] 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.[34] Ground water contaminated by arsenic, as of 2014, "is still poisoning millions of people in Asia".[35]

Mercury

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

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.[36] 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.[37] 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.[38] 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.[39] Since the Industrial Revolution, mercury levels have tripled in many near-surface seawaters, especially around Iceland and Antarctica.[40]

Dutch Boy white lead paint advertisement, 1912.

Lead

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.[41] Dioscorides, a Greek physician who is thought to have lived in the 1st century CE,[42] wrote that lead "makes the mind give way". Lead was used extensively in Roman aqueducts from about 500 BC to 300 AD.[43] 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."[44] During the Mongol period in China (1271−1368 AD), lead pollution due to silver smelting in the Yunnan region exceeded contamination levels from modern mining activities by nearly four times.[45][n 1] In the 17th and 18th centuries, people in Devon were afflicted by a condition referred to as Devon colic; this was discovered to be due to the imbibing of lead-contaminated cider. 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.[47] In the U.S. city of Flint, Michigan, lead contamination in drinking water has been an issue since 2014. The source of the contamination has been attributed to "corrosion in the lead and iron pipes that distribute water to city residents".[48] In 2015, the lead concentration of drinking water in north-eastern Tasmania, Australia, reached a level over 50 times the prescribed national drinking water guidelines. The source of the contamination was attributed to "a combination of dilapidated drinking water infrastructure, including lead jointed pipelines, end-of-life polyvinyl chloride pipes and household plumbing".[49]

Chromium

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

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.[50] In 1890, Newman described the elevated cancer risk of workers in a chromate dye company.[51] Chromate-induced dermatitis was reported in aircraft workers during World War II.[52] 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.[53] 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.[54]

99.999% purity cadmium bar and 1 cm3 cube.

Cadmium

Cadmium exposure is a phenomenon of the early 20th century, and onwards. In Japan in 1910, the Mitsui Mining & Smelting Company began discharging cadmium into the Jinzū 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".[55] In 1955, cadmium was identified as the likely cause and in 1961 the source was directly linked to mining operations in the area.[56] In February 2010, cadmium was found in Walmart exclusive Miley Cyrus jewelry. Wal-Mart continued to sell the jewelry until May, when covert testing organised by Associated Press confirmed the original results.[57] 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.[58]

Remediation

A metal EDTA anion. Pb displaces Ca in Na2[CaEDTA] to give Na2[PbEDTA], which is passed out of the body in urine.[59]

In humans, heavy metal poisoning is generally treated by the administration of chelating agents.[60] These are chemical compounds, such as CaNa2EDTA (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.[61]

Soils contaminated by heavy metals can be remediated 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 toxic 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.[62]

Benefits

Some elements otherwise regarded as toxic heavy metals are essential, in small quantities, for human health. These elements include vanadium, manganese, iron, cobalt, copper, zinc, selenium, strontium and molybdenum.[63] A deficiency of these essential metals may increase susceptibility to heavy metal poisoning.[64]

See also

  • Bento Rodrigues dam disaster
  • Heavy metal detoxification
  • Kingston Fossil Plant coal fly ash slurry spill
  • Light metal
  • Metal toxicity

Explanatory notes

  1. ↑ Up to one-sixth of China's arable land might be affected by heavy metal contamination.[46]

Citations

  1. ↑ Dewan 2008
  2. ↑ Dewan 2009
  3. ↑ Poovey 2001
  4. ↑ Zhang, Hongling; Walker, Tony R.; Davis, Emily; Ma, Guofeng (September 2019). "Ecological risk assessment of metals in small craft harbour sediments in Nova Scotia, Canada". Marine Pollution Bulletin 146: 466–475. doi:10.1016/j.marpolbul.2019.06.068. PMID 31426182. 
  5. ↑ Srivastava & Goyal 2010, p. 2
  6. ↑ Brathwaite & Rabone 1985, p. 363
  7. ↑ "10 chemicals of public health concern" (in en). https://www.who.int/news-room/photo-story/photo-story-detail/10-chemicals-of-public-health-concern. 
  8. ↑ Wright 2002, p. 288
  9. ↑ Qureshi, Shabnam; Richards, Brian K.; McBride, Murray B.; Baveye, Philippe; Steenhuis, Tammo S. (2003). "Temperature and Microbial Activity Effects on Trace Element Leaching from Metalliferous Peats". Journal of Environmental Quality 32 (6): 2067–75. doi:10.2134/jeq2003.2067. PMID 14674528. 
  10. ↑ "Fear In The Fields -- How Hazardous Wastes Become Fertilizer -- Spreading Heavy Metals On Farmland Is Perfectly Legal, But Little Research Has Been Done To Find Out Whether It's Safe". https://archive.seattletimes.com/archive/?date=19970703&slug=2547772. 
  11. ↑ https://hazwastehelp.org/ArtHazards/glassworking.aspx Art Hazards
  12. ↑ Harvey, Handley & Taylor 2015
  13. ↑ Howell et al. 2012; Cole et al. 2011, pp. 2589‒2590
  14. ↑ Finch, Hillyer & Leopold 2015, pp. 849–850
  15. ↑ Aggrawal 2014, p. 680
  16. ↑ Di Maio 2001, p. 527
  17. ↑ Lovei 1998, p. 15
  18. ↑ Perry & Vanderklein 1996, p. 336
  19. ↑ Houlton 2014, p. 50
  20. ↑ Balasubramanian, He & Wang 2009, p. 476
  21. ↑ Worsztynowicz & Mill 1995, p. 361
  22. ↑ Camobreco, Vincent J.; Richards, Brian K.; Steenhuis, Tammo S.; Peverly, John H.; McBride, Murray B. (November 1996). "Movement of heavy metals through undisturbed and homogenized soil columns". Soil Science 161 (11): 740–750. doi:10.1097/00010694-199611000-00003. Bibcode: 1996SoilS.161..740C. 
  23. ↑ Radojevic & Bashkin 1999, p. 406
  24. ↑ Guney, Mert; Zagury, Gerald J. (4 January 2014). "Bioaccessibility of As, Cd, Cu, Ni, Pb, and Sb in Toys and Low-Cost Jewelry". Environmental Science & Technology 48 (2): 1238–1246. doi:10.1021/es4036122. PMID 24345102. Bibcode: 2014EnST...48.1238G. open access
  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. ↑ Wanklyn & Chapman 1868, pp. 73–8; Cameron 1871, p. 484
  31. ↑ Blake 1884
  32. ↑ Dueck 2000, pp. 1–3, 46, 53
  33. ↑ Dyer 2009
  34. ↑ Whorton 2011, p. 356
  35. ↑ Notman 2014
  36. ↑ Zhao, Zhu & Sui 2006
  37. ↑ Waldron 1983
  38. ↑ Emsely 2011, p. 326
  39. ↑ Davidson, Myers & Weiss 2004, p. 1025
  40. ↑ New Scientist August 2014, p. 4
  41. ↑ Pearce 2007; Needleman 2004
  42. ↑ Rogers 2000, p. 41
  43. ↑ Gilbert & Weiss 2006
  44. ↑ Prioreschi 1998, p. 279
  45. ↑ Hillman et al. 2015, pp. 3353–3354
  46. ↑ Hillman et al. 2015, p. 3349
  47. ↑ World Health Organization 2013
  48. ↑ Torrice 2016
  49. ↑ Harvey, Handley & Taylor 2015
  50. ↑ Barceloux & Barceloux 1999
  51. ↑ Newman 1890
  52. ↑ Haines & Nieboer 1988, p. 504
  53. ↑ National Research Council 1974, p. 68
  54. ↑ Tovey 2011; Jones 2011; O'Brien & Aston
  55. ↑ Vallero & Letcher 2013, p. 240
  56. ↑ Vallero & Letcher 2013, pp. 239–241
  57. ↑ Pritchard 2010
  58. ↑ Mulvihill & Pritchard 2010
  59. ↑ Cs uros 1997, p. 124
  60. ↑ Blann & Ahmed 2014, p. 465
  61. ↑ American Cancer Society 2008; National Capital Poison Center 2010
  62. ↑ Evanko & Dzombak 1997, pp. 1, 14–40
  63. ↑ Bánfalvi 2011, p. 12
  64. ↑ Chowdhury 1987

General references



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