A 25-foot (7.6m) 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. Testing showed significantly elevated levels of arsenic, copper, barium, cadmium, chromium, lead, mercury, nickel, and thallium in samples of slurry and river water. Cleanup costs may exceed $1.2 billion.
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.
Contamination sources
Tetraethyl lead is one of the most significant heavy metal contaminants in recent use.
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, (CH 3CH 2) 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]
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 (As 4S 4) and orpiment (As 2S 3), 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]
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]
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-contaminatedcider. 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(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 NewcastleOrica 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 cm 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 Na 2[CaEDTA] to give Na 2[PbEDTA], which is passed out of the body in urine.
In humans, heavy metal poisoning is generally treated by the administration of chelating agents.[60] These are chemical compounds, such as CaNa 2EDTA (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]
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Arsenic is a chemical element with the symbol As and atomic number 33. Arsenic occurs in many minerals, usually in combination with sulfur and metals, but also as a pure elemental crystal. Arsenic is a metalloid. It has various allotropes, but only the gray form, which has a metallic appearance, is important to industry.
Environmental remediation deals with the removal of pollution or contaminants from environmental media such as soil, groundwater, sediment, or surface water. Remedial action is generally subject to an array of regulatory requirements, and may also be based on assessments of human health and ecological risks where no legislative standards exist, or where standards are advisory.
Bioremediation broadly refers to any process wherein a biological system, living or dead, is employed for removing environmental pollutants from air, water, soil, flue gasses, industrial effluents etc., in natural or artificial settings. The natural ability of organisms to adsorb, accumulate, and degrade common and emerging pollutants has attracted the use of biological resources in treatment of contaminated environment. In comparison to conventional physicochemical treatment methods bioremediation may offer considerable advantages as it aims to be sustainable, eco-friendly, cheap, and scalable. Most bioremediation is inadvertent, involving native organisms. Research on bioremediation is heavily focused on stimulating the process by inoculation of a polluted site with organisms or supplying nutrients to promote the growth. In principle, bioremediation could be used to reduce the impact of byproducts created from anthropogenic activities, such as industrialization and agricultural processes. Bioremediation could prove less expensive and more sustainable than other remediation alternatives.
Environmental chemistry is the scientific study of the chemical and biochemical phenomena that occur in natural places. It should not be confused with green chemistry, which seeks to reduce potential pollution at its source. It can be defined as the study of the sources, reactions, transport, effects, and fates of chemical species in the air, soil, and water environments; and the effect of human activity and biological activity on these. Environmental chemistry is an interdisciplinary science that includes atmospheric, aquatic and soil chemistry, as well as heavily relying on analytical chemistry and being related to environmental and other areas of science.
Phytoremediation technologies use living plants to clean up soil, air and water contaminated with hazardous contaminants. It is defined as "the use of green plants and the associated microorganisms, along with proper soil amendments and agronomic techniques to either contain, remove or render toxic environmental contaminants harmless". The term is an amalgam of the Greek phyto (plant) and Latin remedium. Although attractive for its cost, phytoremediation has not been demonstrated to redress any significant environmental challenge to the extent that contaminated space has been reclaimed.
Dimercaprol, also called British anti-Lewisite (BAL), is a medication used to treat acute poisoning by arsenic, mercury, gold, and lead. It may also be used for antimony, thallium, or bismuth poisoning, although the evidence for those uses is not very strong. It is given by injection into a muscle.
Industrial wastewater treatment describes the processes used for treating wastewater that is produced by industries as an undesirable by-product. After treatment, the treated industrial wastewater may be reused or released to a sanitary sewer or to a surface water in the environment. Some industrial facilities generate wastewater that can be treated in sewage treatment plants. Most industrial processes, such as petroleum refineries, chemical and petrochemical plants have their own specialized facilities to treat their wastewaters so that the pollutant concentrations in the treated wastewater comply with the regulations regarding disposal of wastewaters into sewers or into rivers, lakes or oceans. This applies to industries that generate wastewater with high concentrations of organic matter, toxic pollutants or nutrients such as ammonia. Some industries install a pre-treatment system to remove some pollutants, and then discharge the partially treated wastewater to the municipal sewer system.
Hexavalent chromium (chromium(VI), Cr(VI), chromium 6) is chromium in any chemical compound that contains the element in the +6 oxidation state (thus hexavalent). Virtually all chromium ore is processed via hexavalent chromium, specifically the salt sodium dichromate. Hexavalent chromium is key to all materials made from chromium. Approximately 136,000 tonnes (150,000 tons) of hexavalent chromium were produced in 1985.
Ecotoxicology is the study of the effects of toxic chemicals on biological organisms, especially at the population, community, ecosystem, and biosphere levels. Ecotoxicology is a multidisciplinary field, which integrates toxicology and ecology.
Soil contamination, soil pollution, or land pollution as a part of land degradation is caused by the presence of xenobiotic (human-made) chemicals or other alteration in the natural soil environment. It is typically caused by industrial activity, agricultural chemicals or improper disposal of waste. The most common chemicals involved are petroleum hydrocarbons, polynuclear aromatic hydrocarbons, solvents, pesticides, lead, and other heavy metals. Contamination is correlated with the degree of industrialization and intensity of chemical substance. The concern over soil contamination stems primarily from health risks, from direct contact with the contaminated soil, vapour from the contaminants, or from secondary contamination of water supplies within and underlying the soil. Mapping of contaminated soil sites and the resulting cleanups are time-consuming and expensive tasks, and require expertise in geology, hydrology, chemistry, computer modeling, and GIS in Environmental Contamination, as well as an appreciation of the history of industrial chemistry.
Phytotoxicity describes any adverse effects on plant growth, physiology, or metabolism caused by a chemical substance, such as high levels of fertilizers, herbicides, heavy metals, or nanoparticles. General phytotoxic effects include altered plant metabolism, growth inhibition, or plant death. Changes to plant metabolism and growth are the result of disrupted physiological functioning, including inhibition of photosynthesis, water and nutrient uptake, cell division, or seed germination.
Metal toxicity or metal poisoning is the toxic effect of certain metals in certain forms and doses on life. Some metals are toxic when they form poisonous soluble compounds. Certain metals have no biological role, i.e. are not essential minerals, or are toxic when in a certain form. In the case of lead, any measurable amount may have negative health effects. It is often thought that only heavy metals can be toxic, but lighter metals such as beryllium and lithium may also be in certain circumstances. Not all heavy metals are particularly toxic, and some are essential, such as iron. The definition may also include trace elements when abnormally high doses may be toxic. An option for treatment of metal poisoning may be chelation therapy, a technique involving the administration of chelation agents to remove metals from the body.
Environmental toxicology is a multidisciplinary field of science concerned with the study of the harmful effects of various chemical, biological and physical agents on living organisms. Ecotoxicology is a subdiscipline of environmental toxicology concerned with studying the harmful effects of toxicants at the population and ecosystem levels.
Environmental effects of mining can occur at local, regional, and global scales through direct and indirect mining practices. Mining can cause in erosion, sinkholes, loss of biodiversity, or the contamination of soil, groundwater, and surface water by chemicals emitted from mining processes. These processes also affect the atmosphere through carbon emissions which contributes to climate change. Some mining methods may have such significant environmental and public health effects that mining companies in some countries are required to follow strict environmental and rehabilitation codes to ensure that the mined area returns to its original state.
Biosorption is a physiochemical process that occurs naturally in certain biomass which allows it to passively concentrate and bind contaminants onto its cellular structure. Biosorption can be defined as the ability of biological materials to accumulate heavy metals from wastewater through metabolically mediated or physico-chemical pathways of uptake. Though using biomass in environmental cleanup has been in practice for a while, scientists and engineers are hoping this phenomenon will provide an economical alternative for removing toxic heavy metals from industrial wastewater and aid in environmental remediation.
Groundwater pollution occurs when pollutants are released to the ground and make their way into groundwater. This type of water pollution can also occur naturally due to the presence of a minor and unwanted constituent, contaminant, or impurity in the groundwater, in which case it is more likely referred to as contamination rather than pollution. Groundwater pollution can occur from on-site sanitation systems, landfill leachate, effluent from wastewater treatment plants, leaking sewers, petrol filling stations, hydraulic fracturing (fracking) or from over application of fertilizers in agriculture. Pollution can also occur from naturally occurring contaminants, such as arsenic or fluoride. Using polluted groundwater causes hazards to public health through poisoning or the spread of disease.
Bangladesh, with an area of 147,570 km2, features a flood plain landscape and several river systems throughout the country. This landscape provides the major natural resources of water, land, fisheries, forests, and wildlife. The country currently faces several environmental issues which threaten these resources, including groundwater metal contamination, increased groundwater salinity, cyclones and flooding, and sedimentation and changing patterns of stream flow due to watershed mismanagement. Some of these, such as the changing patterns of stream flow and presence of lead in groundwater, can be directly correlated with human activity and industrial processes, while others, such as cyclones and flooding are naturally occurring issues. Many of these issues are further exacerbated by climate change, which causes increased occurrence of storms and cyclones and rising sea levels. According to the Notre Dame Global Adaptation Index, Bangladesh is the 43rd most vulnerable country to the effects of climate change, and the 37th least prepared country to address these effects. There has been some government actions taken to address these issues.
Jerome Okon Nriagu is a Nigerian-born, American environmental chemist, academician and researcher. He is Professor Emeritus in the School of Public Health at the University of Michigan. He was formerly a Research Scientist at Environment Canada in the former National Water Research Institute, Burlington, Ontario, and an Adjunct Professor in the Department of Earth Sciences, University of Waterloo, Canada.
The arsenic (As) cycle is the biogeochemical cycle of natural and anthropogenic exchanges of arsenic terms through the atmosphere, lithosphere, pedosphere, hydrosphere, and biosphere. Although arsenic is naturally abundant in the Earth's crust, long-term exposure and high concentrations of arsenic can be detrimental to human health.
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![A metal EDTA anion. Pb displaces Ca in Na
2[CaEDTA] to give Na
2[PbEDTA], which is passed out of the body in urine. Metal-EDTA.svg](http://upload.wikimedia.org/wikipedia/commons/thumb/0/09/Metal-EDTA.svg/170px-Metal-EDTA.svg.png)
