Polychlorinated biphenyls: a pollutant

Polychlorinated biphenyls (PCBs) are either oily liquids or solids and are colorless to light
yellow and are an insoluble xenobiotic aromatic compounds, in which hydrogen atoms of
biphenyl rings are replaced by chlorine atoms, and widely used for a variety of industrial and
commercial applications, including dielectric fluids in transformers and electric capacitors, in
printing inks, adhesives, surface coatings, flame retardants, coolants, lubricants, plasticizers, due
to their high dielectric constant and thermal stability and are present in sediments and soil.
Besides their applications in different industries PCBs are considered as a potential class of
persistent organic pollutants (POPs). Therefore, the production of PCBs is prohibited, and their
use is conditioned by Part II of Annex A of the Stockholm Convention (Karlaganis et al. 2001;
Lallas 2001). PCBs in the environment are transported at low concentrations by air, and the
movement of fresh and marine waters, resulting in a widespread distribution of PCBs across the
globe, including regions where they have never been used. Consequently, this situation has led to
ubiquitous exposure, with a burden on the general population (Jones and de Voogt 1999; Van der
Oost et al. 2003; El-Shahawi et al. 2010). These PCBs have different commercial producers
along with different trade names such as Monsanto industrial chemicals co. (USA) marketed
PCBs under the trade name, Aroclor, Bayer AG (Germany), Clophen, Caffaro (Italy), Pyralene,
Kanegafiichi Chemical co. (Japan), Kanechlor, Prodolec company (France), Phenoclor and
Chemko company (Czechoslovokia), Delor (Passtore et al., 2014 Afghan and Chau 1989).
Production of these compounds are begin in the 1930s, and 1.3-1.5 million tons of PCBs
have been produced worldwide till 1970s, and manufacturing ceases in the United States in
1977 and have been banned in most countries since 1979, in response to the 1976 passing of the
Toxic Substances Control Act (TSCA), which was primarily due to scientific evidences that
showed PCBs accumulate in the environment and could adversely impact human and other biota.
Thus, even though they are no longer manufactured or used by industries, but these contaminants
still represent a global issue because of their stability these pollutants can persist for longer
period of time in the environment, are still emitted from various sources, such as leaks of
existing equipment such as electrical capacitors and ballasts, volatilization from dredging
sediments, and sewage sludge soil application, thereby significantly contaminating the
ecosystem and continue to be encountered as contaminants of concern in the environment
(Erickson, 1997, Tomza-Marciniak et al., 2019). Owing to hydrophobic nature PCBs are tend to
bioaccumulate in adipose tissue (fat) of higher predators, including human beings. Evidences
showed that they have been detected in virtually every compartment of the ecosystem, including
air, water, soil, sediment, and living organisms. In humans, PCBs are commonly detected in
breast milk and blood, with concentrations increasing with age (15, of aken 2010). Furthermore,
the United States Occupational Safety and Health Administration (OSHA) recommends that
exposure to PCBs in the workplace should be lower than 1.0 mg m−3 for products with 42%
chlorine and 0.5 mg m−3 for products with 54% chlorine, as determined as a time-weighted
average (TWA) of up to 8 hours per day and 40 hours per week (ACGIH 2020). Thus, PCBs are
fall in the category of top five organic contaminants that are more toxic to living organisms
according to the Agency for Toxic Substances and Disease Registry (ATSDR). They have been
classified as endocrine disruptors, mainly affecting thyroid hormone function (Longnecker et al.
1997; Brouwer et al. 1999; Safe 2000; Rudel and Perovich 2009). PCBs are also associated with
skin and eye disorders and liver toxicity and have adverse effects on the immune, nervous, and
reproductive systems (Fischer et al. 1998; White and Birnbaum 2009). In addition, exposure to
PCBs during the prenatal period and in childhood has been related to behavioral problems and
negative impacts on brain functions that control language, learning, and memory (Schantz et
al.2003).

History of PCBs
In the world countries namely, France, Italy, USA, Spain, UK, Germany and Japan were
involved in the production of PCBs. In the beginning of 1929 the commercial manufacturing of
PCBs started at Swan Chemical Compnay, which was further purchased by Monsanto Industrial
Chemicals in the year of 1935. After that, number of chlorinated of biphenyl mixtures under the
trade name of Aroclors were formed. During that time, Monsanto was the global market leader
and accounted over half of PCB production worldwide. From 1971-1973, 1 million pounds of
PCB based heat transfer liquid were produced by Geneva Industries (another USA company). In
early 1950s, origin of PCBs in Japan was started, with the distribution of a series of PCBs
mixtures under the name of Kanechlor by Kanegafuchi Chemical Company, Tokyo. Moreover,
Mitsubishi Monsanto Company (Tokyo) started producing PCBs in 1969. The termination of
production and import of PCBs took place in the starting of 1972. In France, production of
PCBs was done by Rhone-poulenc and Atochem, which was further sold by Prodelec under the
names of Phenoclor and Pyralene. Byer AG started producing PCBs in Germany since the early
1930s which was terminated in 1983, and resulting in 1.5 million tons of Clophens of 50 years of
the production journey. Caffaro began manufacturing of PCBs in the year of 1958 and continued
till 1983 in Italy with the names of Fenclor and Apirolio. Italy was found to be a major producer
of Decachlorobiphenyl, 400,000 pounds which is equal to 180,000 kg imported from Italy. SA
Cros and Rhone-Poulenc had the only Spanish PCBs production plant in Flix. In the Newport
factory of Monsanto the PCBs was produced for the European market in 1954. In 1977, the
production was terminated by Monsanto due to ban of production in the USA.
Chemistry of PCBs
The chemical structure of PCB is characterized by the presence of a biphenyl nucleus carrying 1-
10 chlorine atoms, and results in 209 different compounds known as congeners. These 209
possible PCBs congeners differ to each other based of number and position of the chlorines. The
empirical formula of PCBs is C 12H10-nCln, where n= 1-10 and general chemical structure of
chlorinated biphenyls showing numbering system is shown in figure 1.Each congener is
represented a number from 1-209 according to IUPAC nomenclature as detailed in table 1.
Ballschmiter and Zell introduced a numbering system to arrange every congener in IUPAC
(International Union of Pure and Applied Chemistry) hierarchical order in ascending pattern to
gather information about each congener, from monochlorobiphenyl to decachlorobiphenyl.
These numbering are from 1-209 and also known as BZ number. In this system, 2-
chlorobiphenyl denoted by PCB, ….by PCB….. a complete nomenclature is detailed in table 1
Ballschmiter et al., 1992. To refer all the PCBs having same number of chlorines for instance, di-
chlorobiphenyl “homolog” term is used and further homologs with different patterns of
substitution “isomer” term is used. For example, mono-chlorobiphenyl homolog contains 3
isomers, di-chlorobiphenyl, 12, tri-chlorobiphenyl, 24, tetra-chlorobiphenyl, 42, penta-
chlorobiphenyl, 46, hexa-chlorobiphenyl, 42, hepta-chlorobiphenyl, 24, octa-chlorobiphenyl, 12,
nona-chlorobiphenyl, 3, and deca-chlorobiphenyl, 1(Ballschmiter and Zell (1980). Depending
on number of chlorine atoms attached, PCB congeners are sub grouped into two categories: low
chlorinated PCBs and high chlorinated PCBs. PCBs if they contain less than four atoms of
chlorine are fallen in the category of low-chlorinated PCBs and high chlorinated if they contain
more than four chlorine substituents. High chlorinated PCBs are non-volatile in nature and are
difficult to degrade, on the other side, low-chlorinated PCBs are semi-volatile and can be
degrade rapidly. This structural variability has direct consequences on persistence and
bioaccumulation of PCBs in the environment (14-16 toxics).

Physical and chemical properties

Important properties of PCBs are resistance to breakdown by both acids and bases and have
more thermal stability. In general, PCBs are insoluble in aqueous medium and are freely soluble
in non-polar organic solvents and lipids as well, the solubility relies on number of chlorines
attached. Lower chlorinated PCBs are more soluble than the higher chlorinated PCBs. Due to all
these characteristics these compounds undoubtedly contribute to the environmental persistence,
stability of PCBs and made them widely useful in several applications, as dielectric fluids in
transformers and capacitors, heat transfer fluids, and lubricants (EPA 1980b Afghan and Chau
1989). Moreover, mode of transportation of PCBs is atmosphere, as it is reported that mobility of
PCBs in the surrounding is predicted by its octanol-water partition coefficient (log Kow) i.e.
PCB congeners having low chlorine content have lower log Kow, and have been largely
dispersed in air, resulting in a widespread distribution of PCBs in snow and sea water areas far
away from where they were released into the surrounding, such as in the arctic area. Contrary,
soils and sediments are dominated by higher chlorinated PCBs as they have high log Kow value,
>6 and high efficiency to absorb (44 of aken 2010). As a result, to reduce these contaminants
from the soils are found to be difficult task. Furthermore, as PCBs are combustible in nature, and
the by-product produced are hydrochloric acid polychlorinated dibenzodioxins (PCDDs), and
polychlorinated dibenzofurans (PCDFs) (NFPA 1994) (Campanella et al., 2002; Aken et al.,
2010). Properties of some commercial aroclors is summarized in table 2.

Applications of PCBs
Toxic effect of PCBs
Degradation of PCBs- metabolism pathway explain
  Aerobic degradation
 Anaerobic degradation
 Aerobic and anerobic degradation
Future perspective

Reference
USA production
Durfee, R. L. (1976, November). Production and usage of PCBs in the United States. In National
Conference on Polychlorinated Biphenyls (pp. 103-107).

Rudel and…2009
Polychlorinated biphenyl (PCB) use in the US began in 1929 and peaked in the 1970s (Agency for Toxic
Substances and Disease Registry, 2000; Vorhees, 2001). The mixtures of 209 possible PCB congeners
based on the number and position of chlorine atoms were valued for their low flammability and vapor
pressure and used extensively through the 1970s in a wide range of consumer products such as flame
retardants, paints, plastics, adhesives, lubricants, sealants, hydraulic and heat transfer fluids, capacitors,
transformers, vacuum pumps and gas transition turbines (Agency for Toxic Substances and Disease
Registry, 2000; Jamshidi et al., 2007; Vorhees, 2001). Restriction of their use in the US began in the late
1970s through the US EPA Toxic Substance Control Act (US Environmental Protection Agency, 2008;
Vorhees, 2001) though they remain major global pollutants detected in the atmosphere as well as in
human blood and breast milk (Arisawa et al., 2005; Centers for Disease Control and Prevention, 2005;
Longnecker et al., 2003; Turyk et al., 2007). PCB concentrations in air tend to be highest in urban areas
and lower in rural or remote areas (Harner et al., 2004; Jamshidi et al., 2007; Motelay-Massei et al.,
2005; Shen et al., 2006), with congener composition varying from city to city, indicating that local
sources may have a substantial influence on regional values (Shen et al., 2006) (see Fig. 2). There is
evidence of geographic variation in PCB homolog compositions according to latitude, where relative
contributions of tetra-CBs seem to increase with increasing latitude, while penta-CB and hexa-CB
contributions decrease with increase in latitude (Shen et al., 2006). In Fig. 2, concentrations of a single
PCB congener (IUPAC PCB 52) are plotted to enhance comparability across studies. PCB 52 is among the
more volatile of the congeners, so it tends to be readily detected in air. PCB 52 is estimated to comprise
5–10% of the sum of major PCB congeners in two sets of air sampling data (D. Vorhees, S. Harrad,
personal communication). Indoor air exposures to PCBs are considered to be more significant than
outdoor exposures as studies have shown indoor air concentrations to be at least 10 and up to 100,000
times higher than outdoor air concentrations (Fig. 2). Buildings constructed between 1950 and 1979
generally have higher concentrations of PCBs in indoor air (Hazrati and Harrad, 2006). Caulking in older
buildings (pre 1977) is another important source and its presence in schools is of particular concern. For
example, Fig. 2 shows elevated PCB concentrations in several schools and public buildings in Switzerland
and Germany where PCB-containing caulk was used (Gabrio et al., 2000; Kohler et al., 2002, 2005).
Furthermore, Liebl et al. showed that higher air concentrations of lower chlorinated PCB congeners (as
found in PCB contaminated schools) corresponded to increased blood levels of the same PCB congeners
(Liebl et al., 2004). In addition, certain floor finishes that were commercially available for residential use
during the 1950s and 1960s contained PCBs. Rudel et al. (2008) reported elevated PCBs in indoor air,
house dust, and residents’ blood in two homes where the PCB-containing wood finish Fabulon or
‘‘bowling alley wax’’ was reportedly used in the 1960s. Sanding of floors to refinish them increased
exposures substantially (Rudel et al., 2008). PCBs may also leach from old electronic products, and so in
some cases indoor air concentrations can be reduced by properly disposing of old appliances and
fluorescent lighting that is not marked ANo PC(typically installed prior to 1978) (US Environmental
Protection Agency Region 10, 2007; Vorhees, 2001) Researchers have hypothesized that PCBs enter the
atmosphere from environmental media such as soil (Vorhees, 2001), although recent consideration of
chiral signatures indicates that volatization from soil is not a major source of outdoor air PCB
concentrations (Jamshidi et al., 2007). Rather, outdoor air concentrations in urban areas seem to be due
to venting of indoor air (Jamshidi et al., 2007). Although most PCB uses were banned many years ago,
PCBs can still be found in the environment today due to their thermal stability, resistance to microbial
degradation, and chemical inertness (Vorhees, 2001). PCBs tend to bioaccumulate, leading to dietary
exposures through fish, meat, dairy and processed foods (La Rocca and Mantovani, 2006). As PCBs
become less prevalent, PCB levels in blood seem to be decreasing (Link et al., 2005; Sjodin et al., 2004).
A US study found median blood serum levels of PCB-153 of 90 ng/g lipid in 1985–1989 and 35 ng/g lipid
in 2000–2002, with median values steadily decreasing over the years in between (Sjodin et al., 2004).
Some studies have shown a slow decline in ambient PCB concentrations from the 1980s to 1990s
(Vorhees, 2001) though others show no significant decline from 1997 to 2005 (Harrad et al., 2006).
While diet is considered to be the major source of exposure, dietary levels seem to be decreasing faster
than indoor air concentrations, making inhalation an increasingly important route of exposure (Harrad
et al., 2006; Vorhees, 2001). A study of several North Carolina day care centers concluded that
inhalation of PCBs was the major route of exposure to the children, compared with dietary and non-
dietary ingestion (Wilson et al., 2001), and in homes with elevated PCBs in indoor air and house dust,
possibly due to Fabulon wood floor finish applied around 1960, residents had blood PCB concentrations
in the highest 5% of a representative sample of adults in the US (Rudel et al., 2008). PCBs are established
developmental neurotoxicants in humans, with elevated prenatal PCB concentrations being associated
with cognitive deficits in children (Arisawa et al., 2005; Winneke et al., 2002). PCBs are also associated
with thyroid toxicity, effects on immune, reproductive, nervous, and endocrine systems, and cancer
effects including breast cancer (Agency for Toxic Substances and Disease Registry, 2000; Arisawa et al.,
2005; Brody et al., 2007; Turyk et al., 2007; Winneke et al., 2002). Among the 209 PCB congeners,
different congeners are associated with different types of effects; mono-ortho-substituted and co-planar
congener structures show toxicological effects similar to dioxin (Schecter et al., 1994), while ortho-
substituted congeners appear more neurotoxic (Giesy and Kannan, 1998).
Aken 2010
Toxicity of PCBs has been recognized since the 1930s (45): although acute toxicity for adult humans is
rather low, chronic exposure to PCBs induces serious neurobehavioral, immunological, reproductive,
and endocrine disorders in children (46, 47). According to the Department of Health and Human Services
(DHHS), U.S. Environmental Protection Agency (EPA), and International Agency for Research on Cancer
(IARC), PCBs are suspected to be carcinogenic in animals and humans (45, 48, 49). PCBs are listed as EPA
Priority Pollutants (http://oaspub.epa.gov/) and are ranked at the fifth position in the 2007 CERCLA
(Comprehensive Environmental Response, Compensation, and Liability Act) Priority List of Hazardous
Substances (http://www.atsdr.cdc.gov/).
Fischer 1998
Emerging evidence suggests that certain ortho-substituted PCB congeners are partially responsible for
the neurotoxic effects of PCBs, including decreased catecholamine levels in certain brain regions and
behavioral changes in laboratoryanimals (Shain et al., 1991; Seegal et al., 1990, 1991b,c; Schantz et al.,
1995). Behavioral changes and learning deficits have been observed in monkeys (Schantz, 1997), rats
(Pantaleoni et al., 1988), and humans exposed perinatally to environmental PCBs (Jacobson et al., 1990;
Jacobson and Jacobson, 1996; Rogan and Gladen, 1992; Chen and Hsu, 1994; Chen et al., 1994; Huisman
et al., 1995). It is also known that PCBs present in the environment are slowly being biotransformed,
resulting in a higher proportion of non-coplanar congeners present in environmental samples than
originally present in commercial mixtures. The PCBs found in blood and other tissues of humans,
wildlife, and fish exposed via the food chain to environmental PCBs are also primarily non-coplanar
congeners (Patterson et al., 1994; Johansen et al., 1996). The potential for toxicity from exposures to
non-coplanar PCBs has been demonstrated, and information regarding the mechanisms of action of
these compounds is now becoming available. Knowledge of biochemical mechanisms of action for non-
coplanar congeners is required for meaningful risk assessments connected with low-level exposures to
humans and wildlife. The following presentations describe experimental results that represent newer
information regarding the mechanisms involved in the action of non-coplanar PCBs in different biological
systems.