polychlorinated biphenyl polychlorinated biphenyl polychlorinated biphenyls (pcbs) are highly carcinogenic chemical compounds, formerly used in industrial and consumer products, whose production was banned in the united states by the toxic substances control act in 1979 and internationally by the stockholm convention on persistent organic pollutants in 2001. they are organic chlorine compounds with the formula c12h10−xclx; they were once widely used in the manufacture of carbonless copy paper, as heat transfer fluids, and as dielectric and coolant fluids for electrical equipment. polychlorinated biphenyl chemical structure of pcbs. the possible positions of chlorine atoms on the benzene rings are denoted by numbers assigned to the carbon atoms. identifiers cas number 1336-36-3 echa infocard 100.014.226 un number un 2315 comptox dashboard (epa) dtxsid5024267 properties chemical formula c12h10−xclx molar mass variable appearance light yellow or colorless, thick, oily liquids hazards nfpa 704 (fire diamond) 1 2 0 except where otherwise noted, data are given for materials in their standard state (at 25 °c , 100 kpa). infobox references pcb warning label on a power transformer known to contain pcbs 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. moreover, because of their use as a coolant in electric transformers, pcbs still persist in built environments. 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 bromine analogues of pcbs are polybrominated biphenyls (pbbs), which have analogous applications and environmental concerns. an estimated 1.2 million tons have been produced globally. though the federal ban was enforced by the epa as of 1979, pcbs continued to create health problems in later years through their continued presence in soil and sediment, and from products which were made before 1979. in 1988, tanabe estimated 370,000 tons were in the environment globally and 780,000 tons were present in products, landfills and dumps or kept in storage. 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 brand, 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 (see methods of destruction below). 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.: 2 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. however, as they are typically found at much higher levels in biological and environmental samples they also pose health concerns, particularly to developing animals (including humans). as they do not activate the ahr, they are not considered part of the dioxin group. because of their lower overt toxicity, they have typically been of lesser 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 ascarel czech republic and slovakia delor france phenoclor pyralène (both used by prodolec) germany clophen (used by bayer) italy apirolio fenclor japan kanechlor (used by kanegafuchi) santotherm (used by mitsubishi) pyroclor former ussr sovol sovtol united kingdom aroclor xxxx (used by monsanto company) askarel united states aroclor xxxx (used by monsanto company) asbestol askarel bakola131 chlorextol – allis-chalmers trade name dykanol (cornell-dubilier) hydol inerteen (used by westinghouse) noflamol pyranol/pyrenol, clorinol (used in general electric's oil-filled "clorinol"-branded metal can capacitors. utilized from the early 1960s to late 1970s in air conditioning units, seeburg jukeboxes and zenith televisions) saf-t-kuhl therminol fr series (monsanto ceased production in 1971). 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. there are still 21,500 tons of pcbs stored in the easternmost regions of slovakia. 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. modern sources include pigments, which may be used in inks for paper or plastic products. pcbs are also still found in old equipment like capacitors, ballasts, x-ray machine, and other e-waste. 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 including the human body. 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 pcbs into the biosphere and especially into marine environments. pcbs 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