Chemical structure of PCBs. The possible positions of chlorine atoms on the benzene rings are denoted by numbers assigned to the carbon atoms.
| |
| Identifiers | |
|---|---|
| UN number | UN 2315 |
| Properties | |
| C12H10−xClx | |
| Molar mass | Variable |
| Appearance | Light yellow or colorless, thick, oily liquids |
| Hazards | |
| NFPA 704 (fire diamond) | |
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
| |
PCB warning label on a power transformer known to contain PCBs.
A polychlorinated biphenyl (PCB) is an organic chlorine compound with the formula C12H10−xClx. Polychlorinated biphenyls were once widely deployed as dielectric and coolant fluids in electrical apparatus, carbonless copy paper and in heat transfer fluids.
Because of their longevity, PCBs are still widely in use, even
though their manufacture has declined drastically since the 1960s, when a
host of problems were identified. With the discovery of PCBs' environmental toxicity, and classification as persistent organic pollutants, their production was banned by United States federal law in 1978, and by the Stockholm Convention on Persistent Organic Pollutants in 2001. The International Agency for Research on Cancer (IARC), rendered PCBs as definite carcinogens in humans. According to the U.S. Environmental Protection Agency (EPA), PCBs cause cancer in animals and are probable human carcinogens.
Many rivers and buildings, including schools, parks, and other sites,
are contaminated with PCBs and there has been contamination of food
supplies with the substances.
Some PCBs share a structural similarity and toxic mode of action with dioxins. Other toxic effects such as endocrine disruption (notably blocking of thyroid system functioning) and neurotoxicity are known.
The maximum allowable contaminant level in drinking water in the United
States is set at zero, but because of the limitations of water
treatment technologies, a level of 0.5 parts per billion is the de facto level.
The bromine analogues of PCBs are polybrominated biphenyls (PBBs), which have analogous applications and environmental concerns.
Physical and chemical properties
Physical properties
The compounds are pale-yellow viscous liquids. They are hydrophobic, with low water solubilities: 0.0027–0.42 ng/L for Aroclors, but they have high solubilities in most organic solvents, oils, and fats. They have low vapor pressures at room temperature. They have dielectric constants of 2.5–2.7, very high thermal conductivity, and high flash points (from 170 to 380 °C).
The density varies from 1.182 to 1.566 g/cm3.
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.
PCBs do not easily break down or degrade, which made them
attractive for industries. PCB mixtures are resistant to acids, bases,
oxidation, hydrolysis, and temperature change. They can generate extremely toxic dibenzodioxins and dibenzofurans through partial oxidation. Intentional degradation as a treatment of unwanted PCBs generally requires high heat or catalysis.
PCBs readily penetrate skin, PVC (polyvinyl chloride), and latex (natural rubber). PCB-resistant materials include Viton, polyethylene, polyvinyl acetate (PVA), polytetrafluoroethylene (PTFE), butyl rubber, nitrile rubber, and Neoprene.
Structure and toxicity
PCBs are derived from biphenyl, which has the formula C12H10, sometimes written (C6H5)2.
In PCBs, some of the hydrogen atoms in biphenyl are replaced by
chlorine atoms. There are 209 different chemical compounds in which one
to ten chlorine atoms can replace hydrogen atoms. PCBs are typically
used as mixtures of compounds and are given the single identifying CAS number 1336-36-3 . About 130 different individual PCBs are found in commercial PCB products.
Toxic effects vary depending on the specific PCB. In terms of
their structure and toxicity, PCBs fall into two distinct categories,
referred to as coplanar or non-ortho-substituted arene substitution patterns and noncoplanar or ortho-substituted congeners.
Structures of the twelve dioxin-like PCBs
- Coplanar or non-ortho
- The coplanar group members have a fairly rigid structure, with their two phenyl rings in the same plane. It renders their structure similar to polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans, and allows them to act like PCDDs, as an agonist of the aryl hydrocarbon receptor (AhR) in organisms. They are considered as contributors to overall dioxin toxicity, and the term dioxins and dioxin-like compounds is often used interchangeably when the environmental and toxic impact of these compounds is considered.
- Noncoplanar
- Noncoplanar PCBs, with chlorine atoms at the ortho positions can cause neurotoxic and immunotoxic effects, but only at concentrations much higher than those normally associated with dioxins. They do not activate the AhR, and are not considered part of the dioxin group. Because of their lower toxicity, they are of less concern to regulatory bodies.
Di-ortho-substituted, non-coplanar PCBs interfere with intracellular signal transduction dependent on calcium which may lead to neurotoxicity. ortho-PCBs can disrupt thyroid hormone transport by binding to transthyretin.
Alternative names
Commercial PCB mixtures were marketed under the following names:
Brazil
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Japan
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United States
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Aroclor mixtures
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
four-digit number. In general, the first two digits refer to the product
series as designated by Monsanto (e.g. 1200 or 1100 series); the second
two numbers indicate the percentage of chlorine by mass in the mixture.
Thus, Aroclor 1260 is a 1200 series product and contains 60% chlorine
by mass. It is a myth that the first two digits referred to the number
of carbon atoms; the number of carbon atoms do not change in PCBs. The
1100 series was a crude PCB material which was distilled to create the
1200 series PCB product.
The exception to the naming system is Aroclor 1016 which was
produced by distilling 1242 to remove the highly chlorinated congeners
to make a more biodegradable product. "1016" was given to this product
during Monsanto's research stage for tracking purposes but the name
stuck after it was commercialized.
Different Aroclors were used at different times and for different
applications. In electrical equipment manufacturing in the US, 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.
Production
One
estimate (2006) suggested that 1 million tonnes of PCBs had been
produced. 40% of this material was thought to remain in use.
Another estimate put the total global production of PCBs on the order
of 1.5 million tonnes. The United States was the single largest producer
with over 600,000 tonnes produced between 1930 and 1977. The European
region follows with nearly 450,000 tonnes 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. In East region of Slovakia there
is still 21 500 tons of PCBs stored.
Applications
The utility of PCBs is based largely on their chemical stability, including low flammability and high dielectric constant. In an electric arc, PCBs generate incombustible gases.
Use of PCBs is commonly divided into closed and open applications. Examples of closed applications include coolants and insulating fluids (transformer oil) for transformers and capacitors, such as those used in old fluorescent light ballasts, hydraulic fluids, lubricating and cutting oils, and the like. In contrast, the major open application of PCBs was in carbonless copy ("NCR") paper, which even presently results in paper contamination.
Other open applications were as plasticizers in paints and cements, stabilizing additives in flexible PVC coatings of electrical cables and electronic components, pesticide extenders, reactive flame retardants and sealants for caulking, adhesives, wood floor finishes, such as Fabulon and other products of Halowax in the U.S., de-dusting agents, waterproofing compounds, casting agents.
It was also used as a plasticizer in paints and especially "coal tars"
that were used widely to coat water tanks, bridges and other
infrastructure pieces.
Environmental transport and transformations
PCBs have entered the environment through both use and disposal. The environmental fate of PCBs is complex and global in scale.
Water
Because of their low vapour pressure, PCBs accumulate primarily in the hydrosphere, despite their hydrophobicity, in the organic fraction of soil, and in organisms.
The hydrosphere is the main reservoir. The immense volume of water in
the oceans is still capable of dissolving a significant quantity of
PCBs.
As the pressure of ocean water increases with depth, PCBs become
heavier than water and sink to the deepest ocean trenches where they are
concentrated.
Air
A small volume
of PCBs has been detected throughout the earth's atmosphere. The
atmosphere serves as the primary route for global transport of PCBs,
particularly for those congeners with one to four chlorine atoms.
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).
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. In 2008, concentrations as high as 35 ng/m3, 10 times higher than the EPA guideline limit of 3.4 ng/m3, have been documented inside some houses in the U.S.
Volatilization of PCBs in soil was thought to be the primary
source of PCBs in the atmosphere, but research suggests ventilation of
PCB-contaminated indoor air from buildings is the primary source of PCB
contamination in the atmosphere.
Biosphere
In the biosphere, PCBs can be degraded by the sun, 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.
In bacteria, PCBs may be dechlorinated through reductive dechlorination, or oxidized by dioxygenase enzyme. In eukaryotes, PCBs may be oxidized by the cytochrome P450 enzyme.
Biomagnification
is the increasing concentration of a substance, such as a toxic
chemical, in the tissues of tolerant organisms at successively higher
levels in a food chain.
Like many lipophilic toxins, PCBs undergo biomagnification and bioaccumulation primarily due to the fact that they are easily retained within organisms. Plastic pollution, specifically Microplastics,
are a major contributor of PCB's into the biosphere and especially into
marine environments. PCB's concentrate in marine environments because
freshwater systems, like rivers, act as a bridge for plastic pollution
to be transported from terrestrial environments into marine environments. It has been estimated that 88-95% of marine plastic is exported into the ocean by just 10 major rivers.
An organism can accumulate PCBs by consuming other organisms that have
previously ingested PCB's from terrestrial, freshwater, or marine
environments. The concentration of PCB's within an organism will
increase over their lifetime; this process is called bioaccumulation.
PCB concentrations within an organism also change depending upon which trophic level they occupy. When an organism occupies a high trophic level, like orcas or humans, they will accumulate more PCB's than an organism that occupies a low trophic level, like phytoplankton. If enough organisms with a trophic level are killed due to the accumulation of toxins, like PCB, a trophic cascade can occur. PCB's can cause harm to human health or even death when eaten. PCBs can be transported by birds from aquatic sources onto land via feces and carcasses.
Biochemical metabolism
Overview
PCBs undergo xenobiotic biotransformation, a mechanism used to make lipophilic toxins more polar and more easily excreted from the body.
The biotransformation is dependent on the number of chlorine atoms
present, along with their position on the rings. Phase I reactions occur
by adding an oxygen to either of the benzene rings by Cytochrome P450.
The type of P450 present also determines where the oxygen will be
added; phenobarbital (PB)-induced P450s catalyze oxygenation to the
meta-para positions of PCBs while 3-methylcholanthrene (3MC)-induced
P450s add oxygens to the ortho–meta positions. PCBs containing ortho–meta and meta–para
protons can be metabolized by either enzyme, making them the most
likely to leave the organism. However, some metabolites of PCBs
containing ortho–meta protons have increased steric hindrance from the oxygen, causing increased stability and an increased chance of accumulation.
Species dependent
Metabolism
is also dependent on the species of organism; different organisms have
slightly different P450 enzymes that metabolize certain PCBs better than
others. Looking at the PCB metabolism in the liver of four sea turtle
species (green, olive ridley, loggerhead and hawksbill), green and hawksbill sea turtles have noticeably higher hydroxylation
rates of PCB 52 than olive ridley or loggerhead sea turtles. This is
because the green and hawksbill sea turtles have higher P450 2-like
protein expression. This protein adds three hydroxyl groups to PCB 52,
making it more polar and water-soluble. P450 3-like protein expression
that is thought to be linked to PCB 77 metabolism, something that was
not measured in this study.
Temperature dependent
Temperature
plays a key role in the ecology, physiology and metabolism of aquatic
species. The rate of PCB metabolism was temperature dependent in yellow perch (Perca flavescens). In fall and winter, only 11 out of 72 introduced PCB congeners were excreted and had halflives
of more than 1,000 days. During spring and summer when the average
daily water temperature was above 20 °C, persistent PCBs had halflives
of 67 days. The main excretion processes were fecal egestion, growth
dilution and loss across respiratory surfaces. The excretion rate of
PCBs matched with the perch's natural bioenergetics,
where most of their consumption, respiration and growth rates occur
during the late spring and summer. Since the perch is performing more
functions in the warmer months, it naturally has a faster metabolism and
has less PCB accumulation. However, multiple cold-water periods mixed
with toxic PCBs with coplanar chlorine molecules can be detrimental to
perch health.
Sex dependent
Enantiomers
of chiral compounds have similar chemical and physical properties, but
can be metabolized by the body differently. This was looked at in bowhead whales (Balaena mysticetus)
for two main reasons: they are large animals with slow metabolisms
(meaning PCBs will accumulate in fatty tissue) and few studies have
measured chiral PCBs in cetaceans. They found that the average PCB
concentrations in the blubber were approximately four times higher than
the liver; however, this result is most likely age- and sex-dependent.
As reproductively active females transferred PCBs and other poisonous
substances to the fetus, the PCB concentrations in the blubber were
significantly lower than males of the same body length (less than 13
meters).
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, (such as PCBs 77, 126 and 169), 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 regulation, 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.
Exposure and excretion
In
general, people are exposed to PCBs overwhelmingly through food, much
less so by breathing contaminated air, and least by skin contact. 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 for years, with half lives estimated at 10–15 years. PCBs collect in body fat and milk fat. PCBs biomagnify up the food web and are present in fish and waterfowl of contaminated aquifers. Human infants are exposed to PCBs through breast milk or by intrauterine exposure through transplacental transfer of PCBs and are at the top of the food chain.
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. Common symptoms included dermal and ocular lesions, irregular menstrual cycles and lowered immune responses. Other symptoms included fatigue, headaches, coughs, and unusual skin sores. Additionally, in children, there were reports of poor cognitive development.
Women exposed to PCBs before or during pregnancy can give birth to
children with lowered cognitive ability, immune compromise, and motor
control problems.
There is evidence that crash dieters that have been exposed to
PCBs have an elevated risk of health complications. Stored PCBs in the adipose tissue become mobilized into the blood when individuals begin to crash diet.
PCBs 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. In a cross-sectional study, PCBs were found to be negatively associated with testosterone levels in adolescent boys.
High PCB levels in adults have been shown to result in reduced levels of the thyroid hormone triiodothyronine,
which affects almost every physiological process in the body, including
growth and development, metabolism, body temperature, and heart rate.
It also resulted in reduced immunity and increased thyroid disorders.
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. 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); liver, stomach, and thyroid gland injuries (including hepatocarcinoma), and thymocyte apoptosis. Other effects of PCBs in animals include changes in the immune system, behavioral alterations, and impaired reproduction. PCBs that have dioxin-like activity are known to cause a variety of teratogenic effects in animals. Exposure to PCBs causes hearing loss and symptoms similar to hypothyroidism in rats.
Cancer
In 2013, the International Agency for Research on Cancer (IARC) classified dioxin-like PCBs as human carcinogens.
According to the U.S. EPA, PCBs have been shown to cause cancer in
animals and evidence supports a cancer-causing effect in humans. Per the EPA, studies have found increases in malignant melanoma and rare liver cancers in PCB workers.
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". In contrast an association between elevated blood levels of PCBs and non-Hodgkin lymphoma had been previously accepted.
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 reported an association between
environmental levels of PCBs and immune response.
History
Old
power transformers are a major 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.
In 1935, Monsanto Chemical Company (now Solutia Inc) took over commercial production of PCBs from Swann Chemical Company which had begun in 1929. PCBs, originally termed "chlorinated diphenyls", were commercially produced as mixtures of isomers at different degrees of chlorination. The electric industry used PCBs as a non-flammable replacement for mineral oil to cool and insulate industrial transformers and capacitors. PCBs were also commonly used as heat stabilizer in cables and electronic components to enhance the heat and fire resistance of PVC.
In the 1930s, the toxicity associated with PCBs and other chlorinated hydrocarbons, including polychlorinated naphthalenes, was recognized because of a variety of industrial incidents.
Between 1936 and 1937, there were several medical cases and papers
released on the possible link between PCBs and its detrimental health
effects. In 1936 a U.S. Public health
Service official described the 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. In 1937,
a conference about the hazards was organized at Harvard School of Public Health, and a number of publications referring to the toxicity of various chlorinated hydrocarbons were published before 1940.
In 1947 Robert Brown reminded chemists 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".
In 1954 Japan, Kanegafuchi Chemical Co. Ltd. (Kaneka Corporation) first produced PCBs, and continued until 1972.
Through the 1960s Monsanto Chemical Company knew increasingly
more about PCBs' harmful effects on humans and the environment, per
internal leaked documents released in 2002, yet PCB manufacture and use
continued with few restraints until the 1970s.
In 1966, PCBs were determined by Swedish chemist Sören Jensen to be an environmental contaminant. Jensen, according to a 1994 article in Sierra,
named chemicals PCBs, which previously, had simply been called
"phenols" or referred to by various trade names, such as Aroclor,
Kanechlor, Pyrenol, Chlorinol and others. In 1972, PCB production plants
existed in Austria, West Germany, France, the UK, Italy, Japan, Spain, the USSR and the US.
In the early 1970s, Ward B. Stone of the New York State Department of Environmental Conservation
(NYSDEC) first published his findings that PCBs were leaking from
transformers and had contaminated the soil at the bottom of utility
poles.
There have been allegations that Industrial Bio-Test Laboratories engaged in data falsification in testing relating to PCBs. In 2003, Monsanto and Solutia Inc., a Monsanto corporate spinoff, reached a US$700 million settlement with the residents of West Anniston, Alabama who had been affected by the manufacturing and dumping of PCBs.
In a trial lasting six weeks, the jury found that "Monsanto had
engaged in outrageous behavior, and held the corporations and its
corporate successors liable on all six counts it considered – including
negligence, nuisance, wantonness and suppression of the truth."
Existing products containing PCBs which are "totally enclosed uses" such as insulating fluids in transformers and capacitors, vacuum pump fluids, and hydraulic fluid, are allowed to remain in use. 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.
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. 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 because of the contamination. The extent of human health
effects has been debated, in part because of 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.
Two businessmen who knowingly sold the contaminated feed ingredient
received two-year suspended sentences for their role in the crisis.
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.
The pollution resulting from this factory and the case of Anniston, in
the US, 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.
PCBs entered the human food supply by animals grazing on contaminated
pastures near the factory, especially in local veal mostly eaten by
farmers' families. The exposed population showed an elevated risk of Non-Hodgkin lymphoma, but not for other specific cancers.
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.
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.
Republic of Ireland
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.
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.
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.
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.
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.
Kenya
In Kenya, a number of cases have been reported in the 2010s of thieves selling transformer oil, stolen from electric transformers, to the operators of roadside food stalls for use in deep frying. When used for frying, it is reported that transformer oil lasts much longer than regular cooking oil. The downside of this misuse of the transformer oil is the threat to the health of the consumers, due to the presence of PCBs.
Slovakia
The chemical plant Chemko in Strážske (east Slovakia) was an important producer of polychlorinated biphenyls for the former communist bloc (Comecon) until 1984. Chemko contaminated a large part of east Slovakia, especially the sediments of the Laborec river and reservoir Zemplínska šírava.
Slovenia
Between 1962 and 1983, the Iskra Kondenzatorji company in Semič (White Carniola, Southeast Slovenia) manufactured capacitors using PCBs. Due to the wastewater and improperly disposed waste products, the area (including the Krupa and Lahinja
rivers) became highly contaminated with PCBs. The pollution was
discovered in 1983, when the Krupa river was meant to become a water
supply source. The area was sanitized then, but the soil and water are
still highly polluted. Traces of PCBs were found in food (eggs, cow
milk, walnuts) and Krupa is still the most PCB-polluted river in the
world.
Spain
Several cetacean species have very high mean blubber PCB concentrations likely to cause population declines and suppress population recovery. Striped dolphins, bottlenose dolphins and killer whales
were found to have mean levels that markedly exceeded all known marine
mammal PCB toxicity thresholds. The western Mediterranean Sea and the
south-west Iberian Peninsula were identified as “hotspots”.
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, and Penhros landfill site from where it continues to be released in waste water discharges.
United States
Alabama
PCBs (manufactured through most of the 20th century until the early 2000s) originating from Monsanto Chemical Company in Anniston, Alabama were dumped into Snow Creek, which then spread to Choccolocco Creek, then Logan Martin Lake. In the early 2000s, class action lawsuits were settled by local land owners, including those on Logan Martin Lake, and Lay Reservoir (downstream on the Coosa River),
for the PCB pollution. Donald Stewart, former Senator from Alabama,
first learned of the concerns of hundreds of west Anniston residents
after representing a church which had been approached about selling its
property by Monsanto. Stewart went on to be the pioneer and lead
attorney in the first and majority of cases against Monsanto and focused
on residents in the immediate area known to be most polluted. Other
attorneys later joined in to file suits for those outside the main
immediate area around the plant; one of these was the late Johnnie Cochran.
In 2007, the highest pollution levels remained concentrated in Snow and Choccolocco Creeks.
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%.
In 1989, during construction near the Zilwaukee bridge, workers uncovered an uncharted landfill containing PCB-contaminated waste which required $100,000 to clean up.
Much of the Great Lakes area were still heavily polluted with PCBs in 1988, despite extensive remediation work.
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. Workers also dumped PCB oil down factory drains, which contaminated the city sewage treatment plant.
The City of Bloomington gave away the sludge to area farmers and
gardeners, creating anywhere from 200 to 2,000 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.
The 1985 consent decree required Westinghouse to construct an
incinerator that would incinerate PCB-contaminated materials. Because of
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.
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.
Massachusetts
Pittsfield, in western Massachusetts, was home to the General Electric
(GE) transformer, capacitor, and electrical generating equipment
divisions. The electrical generating division built and repaired
equipment that was used to power 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. PCB-containing solid material was widely used as fill, including oxbows of the Housatonic River. Fish and waterfowl who live in and around the river contain significant levels of PCBs and are not safe to eat.
New Bedford Harbor, which is a listed Superfund site, contains some of the highest sediment concentrations in the marine environment.
Investigations into historic waste dumping in the Bliss Corner neighborhood have revealed the existence of PCBs, among other hazardous materials, buried into soil and waste material.
Missouri
In 1982 Martha C. Rose Chemical Inc. began processing and disposing of materials contaminated with PCB's in Holden, Missouri,
a small rural community about 40 miles east of Kansas City. From 1982
until 1986, nearly 750 companies, including General Motors Corp.,
Commonwealth Edison, Illinois Power Co. and West Texas Utilities, sent
millions of pounds of PCB contaminated materials to Holden for disposal.
Instead, according to prosecutors, the company began storing the
contaminated materials while falsifying its reports to the EPA to show
they had been removed. After investigators learned of the deception,
Rose Chemical was closed and filed for bankruptcy. The site had become
the nation's largest waste site for the chemical PCB.
In the four years the company was operational, the EPA inspected it
four times and assessed $206,000 in fines but managed to collect only
$50,000.
After the plant closed the state environmental agency found PCB
contamination in streams near the plant and in the city's sewage
treatment sludge. A 100,000 square-foot warehouse and unknown amounts of
contaminated soil and water around the site had to be cleaned up. Most
of the surface debris, including close to 13 million pounds of
contaminated equipment, carcasses and tanks of contaminated oil, had to
be removed.
Walter C. Carolan, owner of Rose Chemical, and five others pleaded
guilty in 1989 to committing fraud or falsifying documents. Carolan and
two other executives served sentences of less than 18 months; the others
received fines and were placed on probation. Cleanup costs at the site
are estimated at $35 million.
New York
Pollution of the Hudson River is largely due to dumping of PCBs by General Electric from 1947 to 1977. GE dumped an estimated 1.3 million pounds of PCBs into the Hudson River during these years. This pollution caused a range of harmful effects to wildlife and people who eat fish from the river or drink the water.
Love Canal is a neighborhood in Niagara Falls, New York that was heavily contaminated with toxic waste including PCBs. Eighteen Mile Creek in Lockport, New York is an EPA Superfund site for PCBs contamination.
PCB pollution at the State Office Building in Binghamton was responsible for what is now considered to be the first indoor environmental disaster in the United States. In 1981, a transformer explosion in the basement spewed PCBs throughout the entire 18-story building. The contamination was so severe that cleanup efforts kept the building closed for 13 years.
North Carolina
One
of the largest deliberate PCB spills in American history occurred in
the summer of 1978 when 31,000 gallons (117 m^3) of PCB-contaminated oil
were illegally sprayed by the Ward PCB Transformer Company 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",
occurred over 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 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. Burns and sons pleaded
guilty to state and Federal criminal charges; Burns received a three to
five-year prison sentence. Ward was acquitted of state charges in the
dumping, but was sentenced to 18 months prison time for violation of
TSCA.
Cleanup and disposal of the roadside PCBs generated controversy,
as 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. In October 2013, at the request of the South Carolina Department of Health and Environmental Control (SCDHEC), the City of Charlotte, North Carolina decided to stop applying sewage sludge to land while authorities investigated the source of PCB contamination.
In February 2014, the City of Charlotte admitted PCBs have entered their sewage treatment centers as well.
After the 2013 SCDHEC had issued emergency regulations
the City of Charlotte discovered high levels of PCBs entering its
sewage waste water treatment plants, where sewage is converted to sewage
sludge.
The city at first denied it had a problem, then admitted an "event"
occurred in February 2014, and in April that the problem had occurred
much earlier.
The city stated that its very first test with a newly changed test
method revealed very high PCB levels in its sewage sludge farm field
fertilizer. Because of the widespread use of the contaminated sludge,
SCDHEC subsequently issued PCB fish advisories for nearly all streams
and rivers bordering farm fields that had been applied with city waste.
Ohio
The Clyde cancer cluster (also known as the Sandusky County cancer cluster) is a childhood cancer cluster that has affected many families in Clyde, Ohio and surrounding areas. PCBs were found in soil in a public park within the area of the cancer cluster.
In Akron,
Ohio, soil was contaminated and noxious PCB-laden fumes had been put
into the air by an electrical transformer deconstruction operation from
the 1930s to the 1960s.
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.
In 2013, the state environmental regulators issued a rare emergency order, banning all sewage sludge
from being land applied or deposited on landfills, as it contained very
high levels of PCBs. The problem had not been discovered until
thousands of acres of farm land in the state had been contaminated by
the hazardous sludge. A criminal investigation to determine the perpetrator of this crime was launched.
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.
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%) and municipal and industrial discharges (20%).
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. In August 2015 Spokane joined other U.S cities like San Diego and San Jose, California, and Westport, Massachusetts. in seeking damages from Monsanto.
Wisconsin
From 1954 until 1971, the Fox River in Appleton, Wisconsin had PCBs deposited into it from Appleton Paper/NCR, P.H. Gladfelter, 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.
Pacific Ocean
Polychlorinated biphenyls have been discovered in organisms living in the Mariana trench in the Pacific Ocean. Levels were as high as 1,900 nanograms per gram of amphipod tissue in the organisms analyzed.
Regulation
In 1972 the Japanese government banned the production, use, and import of PCBs.
In 1973, the use of PCBs in "open" or "dissipative" sources, such as plasticisers in paints and cements, casting agents, fire retardant fabric treatments and heat stabilizing additives for PVC electrical insulation, adhesives, paints and waterproofing, railroad ties was banned in Sweden.
In 1976, concern over the toxicity and persistence (chemical stability) of PCBs in the environment led the United States Congress to ban their domestic production, effective January 1, 1978, via the Toxic Substances Control Act.
As the agency that was charged with implementing TSCA, the EPA banned
new manufacturing of PCBs, but it allowed their continued use for
electrical equipment for economic reasons. In 1979 and future years, the EPA continued to regulate PCB usage and disposal.
In 1981, the UK banned closed uses of PCBs in new equipment, and
nearly all UK PCB synthesis ceased; closed uses in existing equipment
containing in excess of 5 litres of PCBs were not stopped until December
2000.
Methods of destruction
Physical
PCBs
are technically attractive because of their inertness, which includes
their resistance to combustion. Nonetheless, they can be effectively
destroyed by incineration
at 1000 °C. When combusted at lower temperatures, they convert in part
to more hazardous materials, including dibenzofurans and
dibenzodioxins. When conducted properly, the combustion products are
water, carbon dioxide, and hydrogen chloride.
In some cases, the PCBs are combusted as a solution in kerosene. PCBs
have also been destroyed by pyrolysis in the presence of alkali metal carbonates.
Thermal desorption is highly effective at removing PCBs from soil.
Chemical
PCBs are fairly chemically unreactive, this property being attractive for its application as an inert material. They resist oxidation.
Many chemical compounds are available to destroy or reduce the PCBs. Commonly, PCBs are degraded by basis mixtures of glycols, which displace some or all chloride. Also effective are reductants such as sodium or sodium naphthenide. Vitamin B12 has also shown promise.
Microbial
Some micro-organisms degrade
PCBs by reducing the C-Cl bonds. Microbial dechlorination tends to be
rather slow-acting in comparison to other methods. Enzymes extracted
from microbes can show PCB activity. In 2005, Shewanella oneidensis biodegraded a high percentage of PCBs in soil samples. A low voltage current can stimulate the microbial degradation of PCBs.
Fungal
There is research showing that some ligninolytic fungi can degrade PCBs.
