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Polychlorinated biphenyls

 

Polychlorinated biphenyls

"PCBs" redirects here. For printed circuit boards, see printed circuit board.



Polychlorinated biphenyls (PCBs) were widely used as dielectric and coolant fluids, for example in transformers, capacitors, and electric motors. Due to PCBs' environmental toxicity and classification as a persistent organic pollutant, PCB production was banned by the United States Congress in 1979 and by the Stockholm Convention on Persistent Organic Pollutants in 2001.[1] According to the U.S. Environmental Protection Agency (EPA), PCBs have been shown to cause cancer in animals, and there is also evidence that they can cause cancer in humans.[2] A number of peer-reviewed health studies have shown an association between exposure to PCBs and non-Hodgkin Lymphoma, a frequently fatal form of cancer.[3][4][5] However, other similar studies have found no such link.[6][7][8] Studies of PCB workers have uniformally shown no statistically significant increased rates of deaths from non-Hodgkin Lymphoma.[9][10][11][12][13][14] In 2013, The International Association for Research on Cancer (IARC) determined that the evidence that PCBs cause non-Hodgkin Lymphoma is “limited” and “not consistent.” [15] Institutions devoted to cancer research and treatment such as the American Cancer Society and the Mayo Clinic do not list PCB exposure as a risk factor for non-Hodgkin Lymphoma.

Concerns about the toxicity of PCBs are largely based on compounds within this group that share a structural similarity and toxic mode of action with dioxin. Toxic effects such as endocrine disruption and neurotoxicity are also associated with other compounds within the group. The maximum allowable contaminant level in drinking water in the United States is set at zero, but due to water treatment technologies a level of 0.5 parts per billion is the defacto level.[16]

Physical and chemical properties

PCBs were produced and marketed as mixtures of many congeners. PCB mixtures are characterized by chlorine content. Less-chlorinated PCBs are odorless, tasteless, clear to pale-yellow, viscous liquids, while highly chlorinated mixtures are more viscous and deeper yellow. They are formed by electrophilic chlorination of biphenyl with chlorine gas. PCBs have low water solubilities — 0.0027-0.42 ng/L for Aroclors,[17] and low vapor pressures at room temperature, but they have high solubilities in most organic solvents, oils, and fats. They have high dielectric constants, very high thermal conductivity,[17] high flash points (from 170 to 380 °C)[17] and are chemically fairly inert, being extremely resistant to oxidation, reduction, addition, elimination, and electrophilic substitution.[18] The density varies from 1.182 to 1.566 kg/L.[17] Other physical and chemical properties vary widely across the class. As the degree of chlorination increases, melting point and lipophilicity increase, and vapour pressure and water solubility decrease.[17]

PCBs readily penetrate skin, PVC (polyvinyl chloride), and latex (natural rubber).[19] PCB-resistant materials include Viton, polyethylene, polyvinyl acetate (PVA), polytetrafluoroethylene (PTFE), butyl rubber, nitrile rubber, and Neoprene.[19]

In terms of structural relationship to toxicity, PCBs fall into 2 distinct categories, referred to as coplanar or non-ortho-substituted arene substitution patterns and noncoplanar or ortho-substituted congeners. The coplanar group members have a fairly rigid structure, with the 2 phenyl rings in the same plane. This gives the molecule a structure similar to polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans, and allows it to act in the same way as these molecules as an agonist of the aryl hydrocarbon receptor (AhR) in organisms. These type of PCBs are considered as contributors to overall dioxin toxicity, and the term dioxin is often used interchangeably when the environmental and toxic impact of these compounds is considered. Noncoplanar PCBs, with chlorine atoms at the ortho positions, have not been found to activate the AhR, and are not considered part of the dioxin group; however, studies have indicated some neurotoxic and immunotoxic effects, but at levels much higher than normally associated with dioxins, and thus of much less concern to regulatory bodies.[20]

PCBs are very stable compounds and do not decompose readily. This is due to their chemical inability to oxidize and reduce in the natural environment. Furthermore, PCBs have a long half life (8 to 15 years) and are insoluble in water, which contributes to their stability.[21] Their destruction by chemical, thermal, and biochemical processes is extremely difficult, and presents the risk of generating extremely toxic dibenzodioxins and dibenzofurans through partial oxidation. Intentional degradation as a treatment of unwanted PCBs generally requires high heat or catalysis (see Methods of destruction below).

Alternative names

Commercial PCB mixtures were marketed under the following names.:[17][22]

Applications

PCBs were used as coolants and insulating fluids (transformer oil) for transformers and capacitors, such as those used in old fluorescent light ballasts.[23] PCBs were also used as plasticizers in paints and cements, stabilizing additives in flexible PVC coatings of electrical wiring and electronic components, pesticide extenders, cutting oils, reactive flame retardants, lubricating oils, hydraulic fluids, and sealants (for caulking in schools and commercial buildings[24]), adhesives, wood floor finishes (such as Fabulon and other products of Halowax in the U.S.),[24] paints, de-dusting agents, water-proofing compounds, casting agents, vacuum pump fluids, fixatives in microscopy, surgical implants, and in carbonless copy ("NCR") paper.[17] Because of its use as a plasticizer in paints and especially "coal tars" that were used widely to coat water tanks, bridges and other infrastructure pieces it is recommended that before sandblasting to remove these materials the existing coal tar should be tested first to see if PCB's are indeed present or not.

History

In 1865 the first "PCB-like" chemical was discovered, and was found to be a byproduct of coal tar. Years later in 1881, German chemists synthesized the first PCB in a laboratory. From the initial synthesis of PCB until 1914, large amounts of PCB were released into the environment, to the extent that there are still measurable amounts of PCB in feathers of birds currently held in museums.[25][26]

PCBs, originally termed "chlorinated diphenyls," were commercially produced as complex mixtures containing multiple isomers at different degrees of chlorination. In the United States, commercial production of PCBs was taken over in 1929 by Monsanto Company from Swann Chemical Company. Manufacturing levels increased in response to the electrical industry's need for a safer (than flammable mineral oil) cooling and insulating fluid for industrial transformers and capacitors. PCBs were also commonly used as stabilizing additives in the manufacture of flexible PVC coatings for electrical wiring and electronic components to enhance the heat and fire resistance of the PVC.[27]

The toxicity associated with PCBs and other chlorinated hydrocarbons, including polychlorinated naphthalenes, was recognized very early due to a variety of industrial incidents.[28] Between 1936 and 1937, there were several medical cases and papers released on the possible link between PCBs and its detrimental health effects. One of the earlier cases in 1936 described an incident where a U.S. Public Health Service official described a wife and child of a worker from the Monsanto Industrial Chemical Company who exhibited blackheads and pustules on their skin. The official attributed these symptoms to contact with the worker's clothing after he returned from work.[29] A conference about the hazards was organized at Harvard School of Public Health in 1937, and a number of publications referring to the toxicity of various chlorinated hydrocarbons were published before 1940.[30] Robert Brown reminded chemists in 1947 that Arochlors were "objectionably toxic. Thus the maximum permissible concentration for an 8-hr. day is 1 mg/m3 of air. They also produce a serious and disfiguring dermatitis".[31] However, PCB manufacture and use continued with few restraints until the 1970s.

PCBs are persistent organic pollutants and have entered the environment through both use and disposal. The environmental transport of PCBs is complex and nearly global in scale. The public, legal, and scientific concerns about PCBs arose from research indicating they are likely carcinogens having the potential to adversely impact the environment and, therefore, undesirable as commercial products. Despite active research spanning five decades, extensive regulatory actions, and an effective ban on their production since the 1970s, PCBs still persist in the environment and remain a focus of attention.[17]

The only North American producer, Monsanto Company, marketed PCBs under the trade name Aroclor from 1930 to 1977. These were sold under trade names followed by a 4-digit number. In general, the first two digits refer to the number of carbon atoms in the biphenyl skeleton (for PCBs this is 12); the second two numbers indicate the percentage of chlorine by mass in the mixture. Thus, Aroclor 1260 has 12 carbon atoms and contains 60% chlorine by mass. An exception is Aroclor 1016, which also has 12 carbon atoms, but has 42% chlorine by mass. Different Aroclors were used at different times and for different applications. In electrical equipment manufacturing in the USA, Aroclor 1260 and Aroclor 1254 were the main mixtures used before 1950; Aroclor 1242 was the main mixture used in the 1950s and 1960s until it was phased out in 1971 and replaced by Aroclor 1016.[17]

Manufacture peaked in the 1960s, by which time the electrical industry had lobbied the U.S. Congress to make them mandatory safety equipment. In 1966, they were determined by Swedish chemist Dr. Soren Jensen to be an environmental contaminant,[32] and it was Dr. Jensen, according to a 1994 article in Sierra, who named them PCBs. Previously, they had simply been called "phenols" or referred to by various trade names, such as Aroclor, Kennechlor, Pyrenol, Chlorinol and others.

Their commercial utility was based largely on their chemical stability, including low flammability, and desirable physical properties, including electrical insulating properties. Their chemical and physical stability has also been responsible for their continuing persistence in the environment, and the lingering interest decades after regulations were imposed to control environmental contamination.

In 1972, PCB production plants existed in Austria, the then Federal Republic of Germany, France, Great Britain, Italy, Japan, Spain, USSR, and USA.[17]

In 1973, the use of PCBs was banned[where?] in "open" or "dissipative" sources, such as:

However, they continued to be allowed in "totally enclosed uses" such as transformers and capacitors, which, in certain failure modes or out-of-specification conditions, can leak, catch fire, or explode. It was Ward B. Stone of the New York State Department of Environmental Conservation (NYSDEC) who first published his findings in the early 1970s that PCBs were leaking from transformers and had contaminated the soil at the bottom of utility poles. Concern over the toxicity and persistence (chemical stability) of PCBs in the environment led the United States Congress to ban their domestic production in 1979,[33] although some use continues in closed systems such as capacitors and transformers.

"Enclosed uses" of PCBs include:

In the UK, closed uses of PCBs in new equipment were banned in 1981, when nearly all UK PCB synthesis ceased, but closed uses in existing equipment containing in excess of 5 litres of PCBs were not stopped until December 2000.[34]

In Japan, PCBs were first produced by Kanegafuchi Chemical Co. Ltd. (Kaneka) in 1954 and production continued until 1972 when the Japanese government banned the production, use, and import of PCBs.[17]

Estimates have put the total global production of PCBs on the order of 1.5 million tons. The United States was the single largest producer with over 600,000 tons produced between 1930 and 1977. The European region follows with nearly 450,000 tons through 1984. It is unlikely that a full inventory of global PCB production will ever be accurately tallied, as there were factories in Poland, East Germany, and Austria that produced unknown amounts of PCBs.[35]

Pollution due to PCBs

Belgium

In 1999, the Dioxine affair caused serious trouble for the Belgian government, when PCBs were found in chicken and eggs.

Italy

The production of PCBs was banned in Italy starting in 1983. In that year the only Italian factory that produced PCBs, Caffaro, located in Brescia, went out of business. That company started producing PCBs in 1932 following the acquisition in 1930 from Monsanto of the rights to use the patent. Brescia[36] and Anniston, in the USA, are the largest cases in the world of PCB contamination in water and soil, in terms of the amount of toxic substance dispersed, size of the area contaminated, number of people involved and duration of production.

The values reported by the ASL (local health authority) of Brescia since 1999 are 5,000 times above the limits set by Ministerial Decree 471/1999 (levels for residential areas, 0.001 mg/kg). As a result of this and other investigations, in June 2001, a complaint of an environmental disaster was presented to the Public Prosecutor's Office of Brescia.[37][38] Other sample surveys on the adult population of Brescia showed that residents of some urban areas have PCB levels that are 10-20 times higher than reference values.

Republic of Ireland

In December 2008, a number of Irish news sources reported testing had revealed "extremely high"[39] levels of dioxins, by toxic equivalent, in pork products, ranging from 80 to 200 times the EU's upper safe limit of 1.5 pg WHO-TEQDFP/μg i.e. 0.12 to 0.3 parts per billion.[40][41]

Brendan Smith, the Minister for Agriculture, Fisheries and Food, stated the pork contamination was caused by PCB-contaminated feed that was used on 9 of Ireland's 400 pig farms, and only one feed supplier was involved.[40][42] Smith added that 38 beef farms also used the same contaminated feed, but those farms were quickly isolated and no contaminated beef entered the food chain.[43] While the contamination was limited to just 9 pig farms, the Irish government requested the immediate withdrawal and disposal of all pork-containing products produced in Ireland and purchased since 1 September 2008. This request for withdrawal of pork products was confirmed in a press release by the Food Safety Authority of Ireland on December 6.[44]

It is thought that the incident resulted from the contamination of fuel oil used in a drying burner at a single feed processor, with PCBs. The resulting combustion produced a highly toxic mixture of PCBs, dioxins and furans, which was included in the feed produced and subsequently fed to a large number of pigs.[45]

Slovakia

The chemical plant Chemko in Strážske (east Slovakia) was an important producer of polychlorinated biphenyls for the former communist block (Comecon) until 1984. Chemko contaminated a large part of east Slovakia, especially the sediments of the Laborec river and reservoir Zemplínska šírava.[46][47]

United Kingdom

Monsanto manufactured PCBs at its chemical plant in Newport, South Wales, until the mid- to late-1970s. During this period, waste matter, including PCBs, from the Newport site was dumped at a disused quarry near Groes-faen, west of Cardiff, from where it continues to be released in waste water discharges.[48]

United States

Massachusetts

Pittsfield, in western Massachusetts, was home to the General Electric (GE) transformer and capacitor divisions, and electrical generating equipment built and repaired in Pittsfield powered the electrical utility grid throughout the nation. PCB-contaminated oil routinely migrated from GE's 254-acre (1.03 km2) industrial plant located in the very center of the city to the surrounding groundwater, nearby Silver Lake, and to the Housatonic River, which flows through Massachusetts, Connecticut, and down to Long Island Sound.[49]

PCB-containing solid material was widely used as fill, including oxbows of the Housatonic River.[49] In the 1940s, GE launched a giveaway program in which locals could receive PCB-contaminated material to use as fill. The recipients were required to sign a letter stating they were receiving clean fill and releasing GE for any subsequent problems.[50] Beginning in 1997, the Massachusetts Department of Environmental Protection began evaluating over 700 suspect properties. As of 2010, over 250 properties had been found to have dangerous concentrations of PCBs in soil, and 180 properties had had contaminated soil removed.

New Bedford Harbor, which is a listed Superfund site,[51] contains some of the highest sediment concentrations in the marine environment.[52]

Current Massachusetts drinking water standards for PCBs are 0.0005 mg/L.[53]

New York State

Between approximately 1947 and 1977, GE released between 500,000 lbs and 1,500,000 lbs of PCBs into the Hudson River.[54] The PCBs came from the company's two capacitor manufacturing plants at Hudson Falls and Fort Edward in New York State.[54]

In 1976, because of concern over continuing high levels of PCBs in local fish and other aquatic organisms, and the unacceptable risk to the health of consumers of such fish, the NYSDEC banned all fishing in the upper Hudson River, as well as commercial fishing of striped bass and several other species in the lower Hudson River,[54][55] and also issued advisories restricting the consumption of fish caught within a 20-mile (30 km) long segment of the Hudson River from Hudson Falls to Troy.[54][56]

There have been many programs of remediation work to reduce the PCB pollution. In 1984, approximately 200 miles (320 km) of the Hudson River was designated a Superfund site, and attempts to clean up the upper Hudson River began, including the removal in 1977-8 of 180,000 cubic yards (140,000 m3) of contaminated river sediments near Fort Edward.[55] In 1991, further PCB pollution was found at Bakers Falls, near the former GE Hudson Falls factory, and a program of remediation was started.[55] In August 1995, a 40-mile (64 km) reach of the upper Hudson was reopened to fishing, but only on a catch-and-release basis.[55] Removal of contaminated soil from Rogers Island was completed in December, 1999.[55] In 2002, the United States Environmental Protection Agency (EPA) announced a further 2,650,000 cubic yards (2,030,000 m3) of contaminated sediments in the upper Hudson River would be removed.

North Carolina

One of the largest PCB "spills" in American history occurred in the summer of 1978 when 31,000 gallons of PCB-contaminated oil were criminally and deliberately sprayed in 3-foot (0.91 m) swaths along the roadsides of some 240 miles (390 km) of North Carolina highway shoulders in 14 counties and at the Fort Bragg Army Base. The crime, known as "the midnight dumpings," lasted nearly 2 weeks, as drivers of a black-painted tanker truck drove down one side of rural Piedmont highways spraying their noxious liquid and then up the other side the following night.

Under the direction of Governor James B. Hunt, Jr., state officials then erected large, yellow warning signs along the contaminated highways that read: "CAUTION: PCB Chemical Spills Along Highway Shoulders."

The timing of the PCB crime was important. Toxic waste had become a national concern, and as the PCBs were literally being dumped along the roadsides in North Carolina, the Environmental Protection Agency's Toxic Substance Control Act, (TSCA), which specifically addressed the disposal of PCBs became effective (August 2, 1978). Also, simultaneously, residents of the contaminated Love Canal community were being evacuated from their homes because of an old toxic landfill. The pressure to build new, safer landfills was enormous. The rationale for the midnight dumpings, according to the state's logic, was that new EPA regulations were going to make disposing of PCBs more expensive, and companies might try to save money by disposing of toxic chemicals illegally; therefore, there was a pressing need to build convenient and affordable toxic waste landfills in North Carolina.

Within a couple of weeks of the crime, Robert Burns and his sons, Timothy and Randall, were arrested for dumping the PCBs along the roadsides. Burns was a business partner of Robert "Buck" Ward, Jr., of the Ward PCB Transformer Company, in Raleigh. Ward and Burns eventually did minimal time in jail for their crime because of federal charges; however, state charges were dropped.

While the Governor's plan was to pick up the roadside PCBs and to bury them in a landfill in rural Warren County, one of the most highly contaminated PCB counties, he faced a fierce opposition from residents who didn't want persistent, toxic PCBs to be buried in a landfill, which - according to new TSCA regulations - would be built only a few feet above their water table. For four years, residents of Warren County mounted an opposition to the PCB landfill that would eventuate in a six-week, non-violent direct-action campaign that would launch the environmental justice movement and that would, according to Johns Hopkins Professor Dr. Eileen McGurty, "transform environmentalism." see:Transforming Environmentalism: Warren County, PCBs, and the Origin of Environmental Justice.

Indiana

From the late 1950s through 1977, Westinghouse Electric used PCBs in the manufacture of capacitors in its Bloomington, Indiana plant. Reject capacitors were hauled and dumped in area salvage yards and landfills, including Bennett's Dump, Neal's Landfill and Lemon Lane Landfill.[57] Workers also dumped PCB oil down factory drains, which contaminated the city sewage treatment plant.[58] The City of Bloomington gave away the sludge to area farmers and gardeners, creating anywhere from 200 to 2000 sites, which remain unaddressed. Over 2 million pounds of PCBs were estimated to have been dumped in Monroe and Owen counties. Although federal and state authorities have been working on the sites' environmental remediation, many areas remain contaminated. Concerns have been raised regarding the removal of PCBs from the karst limestone topography, and regarding the possible disposal options. To date, the Westinghouse Bloomington PCB Superfund site case does not have a Remedial Investigation/Feasibility Study (RI/FS) and Record of Decision (ROD), although Westinghouse signed a US Department of Justice Consent Decree in 1985.[57] The 1985 consent decree required Westinghouse to construct an incinerator that would incinerate PCB-contaminated materials. Due to public opposition to the incinerator, however, the State of Indiana passed a number of laws that delayed and blocked its construction. The parties to the consent decree began to explore alternative remedies in 1994 for six of the main PCB contaminated sites.[57]

On 15 February 2008, Monroe County approved a plan to clean up the three remaining contaminated sites in the City of Bloomington, at a cost of $9.6 million to CBS Corp., the successor of Westinghouse.[59]

Great Lakes

In 1976 environmentalists found PCBs in the sludge at Waukegan Harbor, the southwest end of Lake Michigan. They were able to trace the source of the PCBs back to the Outboard Marine Corporation that was producing boat motors next to the harbor. By 1982, the Outboard Marine Corporation was court ordered to released quantitative data referring to their PCB waste released. The data stated that from 1954 they released 100,000 tons of PCB into the environment, and that the sludge contained PCBs in concentrations as high as 50%.[60][61]

Late during the construction of new on- and off-ramps in the M-13 interchange on the Zilwaukee bridge approach, workers uncovered an uncharted landfill containing PCB-contaminated waste, necessitating an environmental cleanup. In August 22, 1989, The Detroit Free Press noted that the clean up costs would cost over $100,000 and delay the opening of the ramps to the M-13 interchange in Zilwaukee, which were scheduled for opening that year.[62]

Much of the Great Lakes area is still heavily polluted with PCBs, despite extensive remediation work.[63] Locally caught fresh water fish and shellfish are contaminated with PCBs, and their consumption is restricted.

Alabama

PCBs (manufactured through most of the 20th century) originating from Monsanto Chemical Company in Anniston, Alabama (Fort McClellan) were dumped into Snow Creek, which then spread to Choccolocco Creek, then Logan Martin Lake. In the early 2000s, class action lawsuits (led, in at least one case, by the late Johnnie Cochran) were settled by local land owners, including those on Logan Martin Lake, and Lay Reservoir (downstream on the Coosa River), for the PCB pollution. Military personnel residing and training at Fort McClellan were not notified of these dangers and were not a party to the settlement.

Today, the highest pollution levels remain concentrated in Snow and Choccolocco Creeks.[64] Concentrations in fish have declined and continue to decline over time; sediment disturbance, however, can resuspend the PCBs from the sediment back into the water column and food web.

South Carolina

From 1955 until 1977, the Sangamo Weston plant in Pickens, SC, used PCBs to manufacture capacitors, and dumped 400,000 pounds of PCB contaminated wastewater into the Twelve Mile Creek. In 1990, the EPA declared the 228 acres (0.92 km2) site of the capacitor plant, its landfills and the polluted watershed, which stretches nearly 1,000 acres (4.0 km2) downstream to Lake Hartwell as a Superfund site. Two dams on the Twelve Mile Creek are to be removed and on Feb. 22, 2011 the first of two dams began to be dismantled. Some contaminated sediment is being removed from the site and hauled away, while other sediment is pumped into a series of settling ponds.[65][66]

In 2013, the State Environmental regulators SCDHEC issued a rare emergency order, banning the land application of sludge as it was discovered that wastewater sludge contained very high levels of PCB's.[67]

Environmental transport and transformations

Due to their low vapour pressure, PCBs accumulate primarily in the hydrosphere, in the organic fraction of soil, and in organisms. Despite their hydrophobicity, the immense volume of water in the oceans is still capable of dissolving a significant quantity of PCBs.

However, a small volume of PCBs has been detected throughout the atmosphere, from the most urbanized areas that are the centers for PCB pollution, to regions north of the Arctic Circle. While the hydrosphere is the main reservoir, the atmosphere serves as the primary route for global transport of PCBs, particularly for those congeners with one to four chlorine atoms.

Atmospheric concentrations of PCBs tend to be lowest in rural areas, where they are typically in the picogram per cubic meter range, higher in suburban and urban areas, and highest in city centres, where they can reach 1 ng/m³ or more. In Milwaukee, an atmospheric concentration of 1.9 ng/m³ has been measured, and this source alone was estimated to account for 120 kg/year of PCBs entering Lake Michigan.[68] Concentrations as high as 35 ng/m³, 10 times higher than the EPA guideline limit of 3.4 ng/m³, have been found inside some houses in the U.S.[24]

Volatilization of PCBs in soil was thought to be the primary source of PCBs in the atmosphere, but recent research suggests ventilation of PCB-contaminated indoor air from buildings is the primary source of PCB contamination in the atmosphere.[69]

In the atmosphere, PCBs may be degraded by hydroxyl radicals, or directly by photolysis of carbon-chlorine bonds (even if this is a less important process).

In biosphere, PCBs can be degraded by either bacteria or eukariotes, but the speed of the reaction depends on both the number and the disposition of chlorine atoms in the molecule: less substituted, meta- or para- substituted PCBs undergo biodegradation faster than more substituted congeners.

In bacteria, PCBs may be dechlorinated through reductive dechlorination, or oxidized by dioxygenase enzyme.

In eukariotes, PCBs may be oxidized by the cytochrome P450 enzyme.

Health effects

The toxicity of PCBs had been known since before its first commercial production through research done by producing companies themselves in the 1930s; however, these conclusions were dismissed as negligible.

The toxicity of PCBs to animals was first noticed in the 1970s, when emaciated seabird corpses with very high PCB body burdens washed up on beaches. Since seabirds may die far out at sea and still wash ashore, the true sources of the PCBs were unknown. Where they were found was not a reliable indicator of where they had died.

The toxicity of PCBs varies considerably among congeners. The coplanar PCBs, known as nonortho PCBs because they are not substituted at the ring positions ortho to (next to) the other ring, (i.e. PCBs 77, 126, 169, etc.), tend to have dioxin-like properties, and generally are among the most toxic congeners. Because PCBs are almost invariably found in complex mixtures, the concept of toxic equivalency factors (TEFs) has been developed to facilitate risk assessment and regulatory control, where more toxic PCB congeners are assigned higher TEF values on a scale from 0 to 1. One of the most toxic compounds known, 2,3,7,8-tetrachlorodibenzo[p]dioxin, is assigned a TEF of 1.[70]

PCBs also have shown toxic and mutagenic effects by interfering with hormones in the body. PCBs, depending on the specific congener, have been shown to both inhibit and imitate estradiol, the main sex hormone in females. Imitation of the estrogen compound can feed estrogen-dependent breast cancer cells, and possibly cause other cancers, such as uterine or cervical. Inhibition of estradiol can lead to serious developmental problems for both males and females, including sexual, skeletal, and mental development issues.

Exposure and excretion

Individuals can be exposed to PCBs through breathing in contaminated air, consuming contaminated food, and by skin contact with old electrical equipment that contain PCBs. Once exposed, some PCBs may change to other chemicals inside the body. These chemicals or unchanged PCBs can be excreted in feces or may remain in a person's body fat or other organs for months. PCBs may also collect in milk fat and be transmitted to infants through breast-feeding.[71]

Signs and symptoms

  • Humans
The most commonly observed health effects in people exposed to extremely high levels of PCBs are skin conditions, such as chloracne and rashes, but these were known to be symptoms of acute systemic poisoning dating back to 1922. Studies in workers exposed to PCBs have shown changes in blood and urine that may indicate liver damage. In Japan in 1968, 280 kg of PCB-contaminated rice bran oil was used as chicken feed, resulting in a mass poisoning, known as Yushō disease, in over 14,000 people.[72] Common symptoms included dermal and ocular lesions, irregular menstrual cycles and lowered immune responses.[73][74][75] Other symptoms included fatigue, headaches, coughs, and unusual skin sores.[76] Additionally, in children, there were reports of poor cognitive development.[73][75][76]
There has been evidence to show crash dieters that have been exposed to PCBs have an elevated risk of health complications. Stored PCBs in the adipose tissue becomes mobilized into the blood when individuals begin to crash diet.[77]
  • Animals
Animals that eat PCB-contaminated food even for short periods of time suffer liver damage and may die. In 1968 in Japan, 400,000 birds died after eating poultry feed that was contaminated with PCBs.[72] Animals that ingest smaller amounts of PCBs in food over several weeks or months develop various health effects, including anemia; acne-like skin conditions (chloracne); and liver, stomach, and thyroid gland injuries (including hepatocarcinoma). Other effects of PCBs in animals include changes in the immune system, behavioral alterations, and impaired reproduction. PCBs are not known to cause birth defects in humans, although those that have dioxin-like activity are known to cause a variety of teratogenic effects in animals.
  • Effects during pregnancy/breastfeeding
Women who were exposed to relatively high levels of PCBs in the workplace or ate large amounts of fish contaminated with PCBs had babies that weighed slightly less than babies from women who did not have these exposures. Babies born to women who ate PCB-contaminated fish also showed abnormal responses in tests of infant behavior. Some of these behaviors, such as problems with motor skills and a decrease in short-term memory, lasted for several years. Other studies suggest that the immune system was affected in children born to and nursed by mothers exposed to increased levels of PCBs. The most likely way infants will be exposed to PCBs is from breast milk. Transplacental transfer causing intrauterine exposure of PCBs were also reported.

Since PCBs accumulate in adipose tissues, mothers exposed to PCBs can pass their exposure to newborn infants through the lipid-rich breast milk produced.[21]

Cancer link

A few studies of workers indicate PCBs were associated with specific kinds of cancer in humans, such as cancer of the liver and biliary tract. It has been hypothesized that PCBs may play a role in the development of cancers of the immune system because some tests of laboratory animals subjected to very high doses of PCBs have shown some effects on the animals’ immune system, and some studies of human populations have purported to find an association between environmental levels of PCBs and immune response.[2][78] However, the subjects of those studies showed normal immune function, and were exposed to numerous other chemicals, such as pesticides, furans, and mercury.[79] Studies of highly exposed PCB workers have shown normal immune function.[80][81][82][83][84] A number of peer-reviewed health studies have also shown an association between elevated blood levels of PCBs and non-Hodgkin lymphoma.[3][4][5] However, other similar studies have found no such association.[7][8][85] Studies of PCB workers have uniformally shown no statistically significant increased rates of deaths from non-Hodgkin Lymphoma.[9][10][11][13][14][86] Studies of laboratory animals subjected to large doses of PCBs have shown no unusual incidence of lymphomas. In 2013, The International Association for Research on Cancer (IARC) determined that the evidence that PCBs cause non-Hodgkin Lymphoma is “limited” and “not consistent.” [15] Institutions devoted to cancer research and treatment do not list PCB exposure as a risk factor for non-Hodgkin Lymphoma.

Mechanism of action

As discussed, PCBs exhibit a wide range of toxic effects. These effects may vary depending on the specific PCB. Similar to dioxin, toxicity of coplanar PCBs and mono-ortho-PCBs are thought to be primarily mediated via binding to aryl hydrocarbon receptor (AhR).[87][88] Because AhR is a transcription factor, abnormal activation may disrupt cell function by altering the transcription of genes. The concept of toxic equivalency factors (TEF) is based on the ability of a PCB to activate AhR.

However, not all effects may be mediated by the AhR receptor, and PCBs do not alter estrogen concentrations to the same degree as other ligands of the AhR receptor, such as PCDD and PCDF, possibly reflecting the reduced potency of PCBs to induce CYP1A1 and CYP1B1.[89] Examples of other actions of PCBs include di-ortho-substituted non-coplanar PCBs interfering with intracellular signal transduction dependent on calcium; this may lead to neurotoxicity.[90] Ortho-PCBs may disrupt thyroid hormone transport by binding to transthyretin.[91]

Congeners that show estrogenic effects bind to the 17 β estradiol receptor. The resulting complex is allowed to enter the nucleus and bind to specific segments of DNA, where it regulates transcription of certain segments of DNA into mRNA. This transcription may not be regulated properly, since it is being controlled by PCBs and not estradiol.

Containment

Because of its difficult containment, many buildings (at least in the U.S.A.) with known high PCB dangers have been evacuated and shut down. In many states, including California, laws require any building with such dangers to be sealed and locked, with large warning signs on every entrance point indicating a PCB presence and also a notice to indicate the presence of chemicals known to cause cancer, health problems or reproductive harm. Until a safe solution can be well established, many of these buildings remain undemolished and sealed. Some forms of containment other than building closure and lockdown are noted below.

Landfill – Large quantities of PCBs have been placed in landfill sites, mainly in the form of transformers and capacitors. Many municipal sites are not designed to contain these pollutants, and thus PCBs are able to escape into the atmosphere or groundwater. No emissions above background are seen if the landfill is designed correctly.

Methods of destruction

These can be separated into three distinct categories: physical, microbial, and chemical destruction.

Physical

Incineration – Although PCBs do not ignite themselves, they can be combusted under extreme and carefully controlled conditions. The current regulations require that PCBs are burnt at a temperature of 1200 °C for at least two seconds, in the presence of fuel oil and excess oxygen.[92] A lack of oxygen can result in the formation of PCDDs, PCDFs and dioxins, or the incomplete destruction of the PCBs. Such specific conditions mean that it is extremely expensive to destroy PCBs on a tonnage scale, and it can only be used on PCB-containing equipment and contaminated liquid. This method is not suitable for the decontamination of affected soils.

Irradiation – If a deoxygenated mixture of PCBs in isopropanol or mineral oil is subjected to irradiation with gamma rays then the PCBs will be dechlorinated to form biphenyl and inorganic chloride. The reaction works best in isopropanol if potassium hydroxide (caustic potash) is added. Solvated electrons are thought to be responsible for the reaction. If oxygen, nitrous oxide, sulfur hexafluoride, or nitrobenzene is present in the mixture then the reaction rate is reduced. This work has been done recently in the US often with used nuclear fuel as the radiation source.[93][94]

Pyrolysis – Destruction of PCBs with pyrolysis using plasma arc processes, like incineration, uses heat. However, unlike incineration, there is no combustion. The long-chain molecules are broken with extreme temperature provided by an electric arc in an inert environment. Adequate post-pyrolysis treatment of the resultant products is required in order to prevent the risk of back reactions.

Microbial

Much recent work has centered on the study of micro-organisms that are able to decompose PCBs. In general, these organisms work in one of two ways: Either they use the PCB as a carbon source or destruction takes place through reductive dechlorination, with the replacement of chlorine with hydrogen on the biphenyl skeleton. However, there are significant problems with this approach. First, these microbes tend to be highly selective in their dechlorination, with lower chlorinated biphenyls being readily transformed, and with preference to dechlorination in the para and meta positions (this is an advantage however, as ortho dechlorination would transform noncoplanar PCBs into dioxin-like coplanar ones). Second, microbial dechlorination tends to be rather slow-acting on PCB as a soil contaminant in comparison to other methods. Last, while microbes work well in laboratory conditions, there is often a problem in transferring a successful laboratory strain to a natural system. This is because the microbes can access other sources of carbon, which they decompose in preference to PCBs.

Further recent developments have focused on testing enzymes and vitamins extracted from microbes that show PCB activity. Especially promising seems to be the use of vitamin B12, in which a cobalt ion is in oxidation state (III) under normal redox conditions. Using titanium (III) citrate as a strong reductant converts the cobalt from Co(III) to Co(I), giving a new vitamin known as B12s, which is a powerful nucleophile and reducing catalyst. This can then be used on PCBs, which it dechlorinates in a rapid and selective manner.[95] In soil samples, Shewanella Oneidenes has biodegraded a high percent of PCB's. [96]

Chemical

Many chemical methods are available to destroy or reduce the toxicity of PCBs.[97]

Nucleophilic aromatic substitution is a method of destroying low-concentration PCB mixtures in oils, such as transformer oil. Substitution of chlorine by polyethylene glycols occurs in under two hours under a blanket of nitrogen, to prevent oxidation of the oil, to produce aryl polyglycols, which are insoluble in the oil and precipitate out.

Between 700 and 925 °C, H2 cleaves the carbon-chlorine bond, and cleaves the biphenyl nucleus into benzene, yielding HCl without a catalyst. This can be performed at lower temperatures with a copper catalyst, and to yield biphenyl. However, since both of these routes require an atmosphere of hydrogen gas and relatively high temperatures, they are prohibitively expensive.

Reaction with highly electropositive metals, or strong reducing agents such as sodium naphthalide, in aprotic solvents results in a transfer of electrons to the PCB, the expulsion of a chloride ion, and a coupling of the PCBs. This is analogous to the Wurtz reaction for coupling halogenoalkanes. The effect is to polymerise many molecules, thereby reducing the volatility, solubility, and toxicity of the mixture. This methodology is most successful on low-strength PCB mixtures and can also be performed electrochemically in a partly aqueous bicontinuous microemulsion.

The solution photochemistry of PCBs is based on the transfer of an electron to a photochemically excited PCB from a species such as an amine, to give a radical anion. This either expels a chloride ion and the resulting aryl radical extracts a hydrogen atom from the solvent or immediately becomes protonated, leading to the loss of a chlorine atom. It is useful only for water-soluble PCBs.

The major pathway for atmospheric destruction of PCBs is via attack by OH radicals. Direct photolysis can occur in the upper atmosphere, but the ultraviolet wavelengths necessary to excite PCBs are shielded from the troposphere by the ozone layer. It has, however, been shown that higher wavelengths of light (> 300 nm) can degrade PCBs in the presence of a photosensitizer, such as acetone.

The Schwartz reaction is the subject of much study, and has significant benefits over other routes. It is advantageous since it proceeds via a reductive process, and thus yields no dioxins through oxidation. The proposed reaction scheme involves the electron transfer from a titanium (III) organometallic species to form a radical anion on the PCB molecule which expels chlorine to eventually form the relatively non-toxic biphenyl.

PCB data

For a complete list of PCB congeners, see PCB Congener List. Note that biphenyl, while not technically a PCB congener due to its lack of chlorine substituents, is still typically included in the literature.

PCB Homolog CASRN Cl Substituents Number of Congeners
Biphenyl 92-52-4 0 1
Monochlorobiphenyl 27323-18-8 1 3
Dichlorobiphenyl 25512-42-9 2 12
Trichlorobiphenyl 25323-68-6 3 24
Tetrachlorobiphenyl 26914-33-0 4 42
Pentachlorobiphenyl 25429-29-2 5 46
Hexachlorobiphenyl 26601-64-9 6 42
Heptachlorobiphenyl 28655-71-2 7 24
Octachlorobiphenyl 55722-26-4 8 12
Nonachlorobiphenyl 53742-07-7 9 3
Decachlorobiphenyl 2051-24-3 10 1

See also

References

External links

  • ATSDR Toxicological Profile U.S. Department of Health and Human Services
  • IARC PCB Monograph
  • US EPA PCB Homepage
  • National Toxicology Program technical reports
  • WHO
  • Case study of plasma arc process for the destruction of PCBs
  • Current Intelligence Bulletin 7: Polychlorinated (PCBs)—NIOSH/CDC
  • Health Canada)


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