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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. Robert Burns and his sons pleaded guilty to state and Federal criminal charages; Robert Burns received a three to five-year prison sentence. Robert Ward was acquitted of state charges in the dumping, but was sentenced to 18 months prison time for violation of the Federal Toxic Substances Control Act.
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. Robert Burns and his sons pleaded guilty to state and Federal criminal charages; Robert Burns received a three to five-year prison sentence. Robert Ward was acquitted of state charges in the dumping, but was sentenced to 18 months prison time for violation of the Federal Toxic Substances Control Act.


Cleanup and disposal of the roadside PCBs has generated considerable controversy. The Governor's plan to pick up the roadside PCBs and to bury them in a landfill in rural [[Warren County, North Carolina|Warren County]] were strongly opposed in 1982 by local residents.<ref>{{cite web |url=http://www.nytimes.com/1982/08/11/us/carolinians-angry-over-pcb-landfill.html |title=CAROLINIANS ANGRY OVER PCB LANDFILL - NYTimes.com |work= |accessdate=}}</ref>
Cleanup and disposal of the roadside PCBs has generated considerable controversy. The Governor's plan to pick up the roadside PCBs and to bury them in a landfill in rural [[Warren County, North Carolina|Warren County]] were strongly opposed in 1982 by local residents.<ref>{{cite web |url=http://www.nytimes.com/1982/08/11/us/carolinians-angry-over-pcb-landfill.html |title=Carolinians Angry Over PCB Landfill|work=NY Times |date=11 August 1982}}</ref>




====South Carolina====
====South Carolina====

Revision as of 21:53, 30 September 2015

"PCBs" redirects here. For printed circuit boards, see printed circuit board.
Chemical structure of PCBs. The possible positions of chlorine atoms on the benzene rings are denoted by numbers assigned to the carbon atoms.
PCB warning label on a power transformer known to contain PCBs.

A polychlorinated biphenyl (PCB; CAS number 1336-36-3 ) is a synthetic organic chemical compound of chlorine attached to biphenyl, which is a molecule composed of two benzene rings. There are 209 configurations of organochlorides with 1 to 10 chlorine atoms. The chemical formula for a PCB is C12H10−xClx. 130 of the different PCB arrangements and orientations are used commercially.[1]

Polychlorinated biphenyls were widely used as dielectric and coolant fluids in electrical apparatus, cutting fluids for machining operations, carbonless copy paper and in heat transfer fluids.[2] 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.[3] According to the U.S. Environmental Protection Agency (EPA), PCBs cause cancer in animals and are probable human carcinogens.[4]

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 de facto level.[5]

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,[1] and low vapor pressures at room temperature, but they have high solubilities in most organic solvents, oils, and fats. They have dielectric constants of 2.5~2.7,[6] very high thermal conductivity,[1] high flash points (from 170 to 380 °C)[1] and are chemically fairly inert, being extremely resistant to oxidation, reduction, addition, elimination, and electrophilic substitution.[7] The density varies from 1.182 to 1.566 kg/L.[1] 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.[1]

PCBs readily penetrate skin, PVC (polyvinyl chloride), and latex (natural rubber).[8] PCB-resistant materials include Viton, polyethylene, polyvinyl acetate (PVA), polytetrafluoroethylene (PTFE), butyl rubber, nitrile rubber, and Neoprene.[8]

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.[9] 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).

Structure and toxicity

In terms of their 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.[10]

Alternative names

Commercial PCB mixtures were marketed under the following names.:[1][11]

Applications

PCBs were used as coolants and insulating fluids (transformer oil) for transformers and capacitors, such as those used in old fluorescent light ballasts.[13] 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[14]), adhesives, wood floor finishes (such as Fabulon and other products of Halowax in the U.S.),[14] paints, de-dusting agents, waterproofing compounds, casting agents, vacuum pump fluids, fixatives in microscopy, surgical implants, and in carbonless copy ("NCR") paper.[1] 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 PCBs are present.

History

Old power transformers are a major legacy source of PCBs. Even units not originally filled with PCB may be contaminated, since PCB and oil mix freely and any given transformer may have been refilled from hoses or tanks also used with PCBs.

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. Between then and 1914, large amounts of PCBs were released into the environment, to the extent that there are still measurable amounts of PCBs in feathers of birds currently held in museums.[15]

PCBs, originally termed "chlorinated diphenyls", were commercially produced as mixtures of isomers at different degrees of chlorination. The electric industry used them as a non-flammable replacement for mineral oil to cool and insulate industrial transformers and capacitors. In the United States, commercial production of PCBs was taken over in 1929 by Monsanto Chemical Company (now Solutia Inc) from Swann Chemical Company. 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.[16]

The toxicity associated with PCBs and other chlorinated hydrocarbons, including polychlorinated naphthalenes, was recognized in the 1930's due to a variety of industrial incidents.[17] 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. 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.[18] 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".[19] Internal leaked documents released post factum show that Monsanto Chemical Company knew increasingly more about the harmful effects of PCBs to humans and the environment through the 1960s, yet PCB manufacture and use continued with few restraints until the 1970s.[20]

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.[1]

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.[1]

In 1966, they were determined by Swedish chemist Dr. Soren Jensen to be an environmental contaminant,[21] 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.[1]

In 1973, the use of PCBs in "open" or "dissipative" sources, such as:

PCB's continue 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.[citation needed] 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,[22] Use continues in closed systems such as capacitors and transformers.[23]

"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.[24]

In Japan, PCBs were first produced by Kanegafuchi Chemical Co. Ltd. (Kaneka Corporation) in 1954 and production continued until 1972 when the Japanese government banned the production, use, and import of PCBs.[1]

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.[25]

Pollution due to PCBs

Belgium

In 1999, the Dioxin Affair occurred when 50 kg of PCB transformer oils were added to a stock of recycled fat used for the production of 500 tonnes of animal feed, eventually affecting around 2,500 farms in several countries.[26][27] The name Dioxin Affair was coined from early misdiagnosis of dioxins as the primary contaminants, when in fact they turned out to be a relatively small part of the contamination caused by thermal reactions of PCBs. The PCB congener pattern suggested the contamination was from a mixture of Aroclor 1260 & 1254. Over 9 million chickens, and 60,000 pigs were destroyed due to the contamination. The extent of human health effects has been debated, in part due to the use of differing risk assessment methods. One group predicted increased cancer rates, and increased rates of neurological problems in those exposed as neonates. A second study suggested carcinogenic effects were unlikely and that the primary risk would be associated with developmental effects due to exposure in pregnancy and neonates.[27] Two businessmen who knowingly sold the contaminated feed ingredient received two-year suspended sentences for their role in the crisis.[28]

Italy

The Italian company Caffaro, located in Brescia, specialized in producing PCBs from 1938 to 1984, following the acquisition of the exclusive rights to use the patent in Italy from Monsanto.[citation needed] The pollution resulting from this factory and the case of Anniston, in the USA, are the largest known 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 local health authority (ASL) 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. Research on the adult population of Brescia showed that residents of some urban areas, former workers of the plant, and consumers of contaminated food, have PCB levels in their bodies that are in many cases 10-20 times higher than reference values in comparable general populations.[29]

PCBs entered the human food supply by animals grazing on contaminated pastures near the factory, especially in local veal mostly eaten by farmers' families.[30] The exposed population showed an elevated risk of Non-Hodgkin lymphoma, but not for other specific cancers.[31]

Japan

In 1968, a mixture of dioxins and PCBs got into rice bran oil produced in northern Kyushu. Contaminated cooking oil sickened more than 1860 people. The symptoms were called Yushō disease.[32]

In Okinawa, high levels of PCB contamination in soil on Kadena Air Base were reported in 1987 at thousands of parts per million, some of the highest levels found in any pollution site in the world.[33]

Republic of Ireland

Main article: 2008 Irish pork crisis

In December 2008, a number of Irish news sources reported testing had revealed "extremely high" 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.[34][35]

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.[34][36] 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.[37] 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.[38]

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.[39]

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.[40][41]

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.[42]

United States

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.[43] 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.[citation needed]

In 2007, the highest pollution levels remained concentrated in Snow and Choccolocco Creeks.[44] 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.

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 release 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%.[45][46]

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.[47]

Much of the Great Lakes area were still heavily polluted with PCBs in 1988, despite extensive remediation work.[48] Locally caught fresh water fish and shellfish are contaminated with PCBs, and their consumption is restricted.[49]


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.[50] Workers also dumped PCB oil down factory drains, which contaminated the city sewage treatment plant.[51] 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.[citation needed] 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.[50] 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 in the consent decree. Hundreds of sites remain unaddressed as of 2014. Monroe County will never be PCB-free, as noted in a 2014 Indiana University program about the local contamination.[50]

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. In 1999, Viacom bought CBS, so they are current responsible party for the PCB sites.[52]


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.[53] PCB-containing solid material was widely used as fill, including oxbows of the Housatonic River.[53]

New Bedford Harbor, which is a listed Superfund site,[54] contains some of the highest sediment concentrations in the marine environment.[55]

Current Massachusetts drinking water standards for PCBs are 0.0005 mg/L.[56]

New York

Main article: Pollution of the Hudson River

Pollution of the Hudson River is water pollution of the Hudson River and pollution of the parts of the Hudson River Valley affected by this water pollution.

The most discussed pollution of the Hudson River is General Electric's contamination of the river with Polychlorinated biphenyls (PCBs) between 1947-77.[57] GE dumped an estimated 1.3 million pounds of PCBs into the Hudson River during these years.[58] This pollution caused a range of harmful effects to wildlife and people who eat fish from the river or drink the water.[57] In response to this contamination, activists protested in various ways. Musician Pete Seeger founded the Hudson River Sloop Clearwater and the Clearwater Festival to draw attention to the problem. The activism led to the site being designated as the nation's largest superfund site.[59] Other kinds of pollution, including mercury contamination and sewage dumping, have caused problems also.[60][61]

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 illegally 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 PCB-laden waste 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 illegal dumping is believed to have been motivated by the passing of the Toxic Substances Control Act (TSCA), which became effective on August 2, 1978 and increased the expense of chemical waste disposal.

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. Robert Burns and his sons pleaded guilty to state and Federal criminal charages; Robert Burns received a three to five-year prison sentence. Robert Ward was acquitted of state charges in the dumping, but was sentenced to 18 months prison time for violation of the Federal Toxic Substances Control Act.

Cleanup and disposal of the roadside PCBs has generated considerable controversy. The Governor's plan to pick up the roadside PCBs and to bury them in a landfill in rural Warren County were strongly opposed in 1982 by local residents.[62]

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.[63][64]

In 2009, the State Environmental regulators noted fish species in Lake Wateree contained exceptionally high levels of PCB contamination. The contamination was so bad that authorities posted adviseries that fish from the lake were unsafe to eat.

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 PCBs.[65]

In 2013 PCBs were discovered in very high levels in wastewater sewage sludge in South Carolina. The problem was not discovered until thousands of acres of farm land in the state were contaminated by this hazardous material. An ongoing criminal investigation is underway to determine the perpetrator of this crime. While investigation was underway, SCDHEC issued emergency regulatory order banning all PCB laden sewage sludge from being land applied on farm fields or deposited into landfills.[65][66]

At the request of the SCDHEC, the City of Charlotte, North Carolina decided to stop land applying sewage sludge in South Carolina while authorities investigated the source of PCB contamination.[67] In February 2014, the City of Charlotte admits PCBs have entered their sewage treatment centers as well.[68]

In 2014, after SCDHEC passed emergency regulations,[69] the City of Charlotte discovered high levels of PCB's entering its sewage waste water treatment plants, where sewage is converted to sewage sludge (aka biosolids).[70] The city at first denied it had a problem, then admitted an "event" occurred in February 2014, and later admitted the problem occurred much earlier.[71][72] The city admitted that its very first test with the newly changed test method revealed very high PCB levels in its sewage sludge farm field fertilizer. Due to the wide spread use of this contaminated material, SCDHEC subsequently issued PCB fish advisories for nearly all streams and rivers bordering farm fields that had been applied with city waste.[73]

Washington

As of 2015, several bodies of water in the state of Washington were contaminated with PCBs, including the Columbia River. the Duwamish River, Green Lake, Lake Washington, the Okanogan River, Puget Sound, the Spokane River, the Walla Walla River, the Wenatchee River, and the Yakima River.[74]16 May 2024 A study by Washington State published in 2011 found that the two largest sources of PCB flow into the Spokane River were City of Spokane stormwater (44%), municipal and industrial discharges (20%).[75] PCBs entered the environment through paint, hydraulic fluids, sealants, inks and have been found in river sediment and wild life. Spokane utilities will spend $300 million to prevent PCBs from entering the river in anticipation of a 2017 federal deadline to do so./[76] In August 2015 Spokane joined other U.S cities like San Diego and San Jose, California, and Westport, Massachusetts. in seeking damages from Monsanto.[77]

Wisconsin

From 1954 until 1971, The Fox River in Appleton, WI had PCBs deposited into it from Appleton Paper/NCR, P.H. Gladfelter, and Georgia Pacific and other notable local paper manufacturing facilities. The Wisconsin DNR estimates that after wastewater treatment the PCB discharges to the Fox River due to production losses ranged from 81,000 kg to 138,000 kg. (178,572 lbs. to 304,235 lbs) The production of Carbon Copy Paper and its byproducts led to the discharge into the river. Fox River clean up is ongoing[78]

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.[citation needed] Despite their hydrophobicity, the immense volume of water in the oceans is still capable of dissolving a significant quantity of PCBs.[citation needed]

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.[citation needed]

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.[79] 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.[14]

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.[80]

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).[citation needed]

In biosphere, PCBs can be degraded by either bacteria or eukaryotes, 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.[citation needed]

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

In eukaryotes, PCBs may be oxidized by the cytochrome P450 enzyme.[citation needed]

Health effects

Labelling transformers containing PCBs

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, a PCDD, is assigned a TEF of 1.[81]

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.[citation needed]

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.[82]

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 1800 people.[32] Common symptoms included dermal and ocular lesions, irregular menstrual cycles and lowered immune responses.[83][84][85] Other symptoms included fatigue, headaches, coughs, and unusual skin sores.[86] Additionally, in children, there were reports of poor cognitive development.[83]
There is significant evidence that women exposed to PCBs before or during pregnancy can give birth to children with lowered cognitive ability, immune compromise, and motor control problems.[87][88][89] 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.[9]
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.[90]
  • 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.[91] 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).[citation needed] Other effects of PCBs in animals include changes in the immune system, behavioral alterations, and impaired reproduction.[citation needed] PCBs that have dioxin-like activity are known to cause a variety of teratogenic effects in animals.

Cancer link

In 2013, the International Agency for Research on Cancer classified PCBs as human carcinogens.[92] According to the EPA, PCBs have been shown to cause cancer in animals and evidence supports a cancer-causing effect in humans.[4] Per EPA, studies have found increases in malignant melanoma and rare liver cancers in PCB workers.[4]

As of 2012, a review has shown an association between elevated blood levels of PCBs and non-Hodgkin lymphoma.[93] while studies of PCB workers showed no increased death rates from non-Hodgkin Lymphoma.[94] In 2013, the International Association for Research on Cancer (IARC) determined that the evidence for PCBs causing non-Hodgkin Lymphoma is "limited" and "not consistent".[92] 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).[95][96] 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.[97] Ortho-PCBs may disrupt thyroid hormone transport by binding to transthyretin.[98] 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 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.[4]

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.[citation needed] 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.

Large quantities of PCBs have been placed in landfills, 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.[citation needed]

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.[99][dead link] 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.[citation needed]

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.[100][101]

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.[citation needed]

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.[citation needed] A low voltage current can stimulate the microbial degradation of PCBs.[102]

Enzymes and vitamins extracted from microbes that show PCB activity have been tested for use in biodegradation. 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, a powerful nucleophile and reducing catalyst can then be used on PCBs,[where?] which it dechlorinates in a rapid and selective manner.[103] In 2005, Shewanella oneidensis biodegraded a high percent of PCBs in soil samples.[104]

Chemical

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

Homologs

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

Wikimedia Commons has media related to Polychlorinated biphenyls.

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