Polychlorinated biphenyl Totally Explained

Everything about Polychlorinated Biphenyls totally explained

Polychlorinated biphenyls (PCBs) are a class of organic compounds with 1 to 10 chlorine atoms attached to biphenyl which is a molecule composed of two benzene rings each containing six carbon atoms. The chemical formula for all PCBs is C₁₂H_10-xCl_x.
PCBs were used as coolants and insulating fluids for transformers and capacitors, stabilizing additives in flexible PVC coatings of electrical wiring and electronic components, pesticide extenders, cutting oils, flame retardants, hydraulic fluids, sealants (used in caulking, etc), adhesives, wood floor finishes, paints, de-dusting agents, and in carbonless copy paper. Commercial PCBs preparations are usually mixtures of 50 or more PCB congeners. The density varies from 1.182 to 1.566 kg/L. PCB-resistant materials include Viton, polyethylene, polyvinyl acetate (PVA), polytetrafluoroethylene (PTFE), butyl rubber, nitrile rubber, and Neoprene.

Applications

PCBs were used as coolants and insulating fluids for transformers and capacitors, 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, sealants (for caulking in schools and commercial buildings
   The toxicity associated with PCBs and other chlorinated hydrocarbons, including polychlorinated naphthalenes was recognized very early due to a variety of industrial incidents . 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 . Robert Brown reminded chemists in 1947 that Arochlors were "objectionably toxic. Thus the maximum permissible concentration for an 8-hr. day is 1 mg. per cu.m. of air. They also produce a serious and disfiguring dermatitis." However, PCB manufacture and use continued with few restraints until the 1970s.
   PCBs are persistent organic pollutants and have entered the environment through both use and disposal. The environmental transport of PCBs is complex and nearly global in scale. The public, legal, and scientific concerns about PCBs arose from research indicating they were 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., and it was Dr. Jensen, according to a 1994 article in Sierra, who named them. Previously, they'd simply been called "phenols" or referred to by various trade names, such as Aroclor, Kennechlor, Pyrenol, Chlorinol and others. However, Arochlors (chlorinated biphenyls) were known toxins by 1947. 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, then Federal Republic of Germany, France, Great Britain, Italy, Japan, Spain, USSR, and USA. In Japan, PCBs were first produced by Kanegafuchi Chemical Co. Ltd. (Kaneka) in 1954 and production continued until 1972 when the Japanese government banned the production, use, and import of PCBs.

Large-scale environmental contamination incidents

New York State

In the United States of America, the General Electric Company (GE) released up to of PCBs into the Hudson River between approximately 1947 and 1977. The PCBs came from the company's two capacitor manufacturing plants at Hudson Falls and Fort Edward in New York State.
There have been many programs of remediation work to reduce the PCB pollution, mostly paid for by GE. In 1984, approximately of the Hudson River was designated a Superfund site, and attempts to cleanup the Upper Hudson River began, including the removal in 1977-8 of of contaminated river sediments near Fort Edward.

The Great Lakes

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

Global transport through atmospheric pollution

PCBs have been detected globally in the atmosphere, from the most urbanized areas that are the centers for PCB pollution, to regions north of the Arctic Circle. The atmosphere serves as the primary route for global transport of PCBs, particularly for those congeners with 1 to 4 chlorine atoms.
Atmospheric concentrations of PCBs tend to be lowest in rural areas, where they're 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. 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.

Health effects

The toxicity of PCBs to animals was first noticed in the 1970s when emaciated seabird corpses with very high PCB body burdens washed up on beaches. Since seabirds may die far out at sea and still wash ashore, the true sources of the PCBs were unknown. Where they were found is no reliable indicator of where they'd died.
The toxicity of PCBs varies considerably among congeners. The coplanar PCBs, known as non-ortho PCBs because they're not substituted at the ring positions ortho to (next to) the other ring, (for example 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. One of the most toxic compounds known,, is assigned a TEF of 1.

Signs and symptoms

Humans � The most commonly observed health effects in people exposed to PCBs are skin conditions such as chloracne and rashes, but these were known to be symptoms of systemic poisoning dating back to the 1920s. Studies in workers exposed to PCBs have shown changes in blood and urine that may indicate liver damage. In 1968 in Japan, PCB contamination in rice bran oil caused a mass poisoning known as Yushō Disease in over 14000 people. Common symptoms included dermal and ocular lesions, irregular menstrual cycles and a lowered immune response. Other symptoms included fatigue, headache, cough, and unusual skin sores. Additionally, in children, there were reports of poor cognitive development. Because AhR is a transcription factor, abnormal activation may disrupt cell function by altering the transcription of genes. The concept of toxic equivalency factors (TEF) is based on the ability of a PCB to activate AhR.
However, not all effects may be mediated by the AhR receptor. For example, di-ortho-substituted non-coplanar PCBs interfere with intracellular signal transduction dependent on calcium; this may lead to neurotoxicity. Ortho-PCBs may disrupt thyroid hormone transport by binding to transthyretin.

Containment

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

Methods of destruction

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

Physical

Incineration – Although PCBs don't 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. 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's extremely expensive to destroy PCBs on a tonnage scale, and it can only be used on PCB containing equipment and contaminated liquid. This method isn't suitable for the decontamination of affected soils. Ultrasound – In a similar process to combustion, high power ultrasonic waves are applied to water, generating cavitation bubbles. These then implode or fragment, creating microregions of extreme pressures and temperatures where the PCBs are destroyed. Water is thought to undergo thermolysis, oxidising the PCBs to CO, CO₂ and hydrocarbons such as biphenyl, with chlorine present as the inorganic ion 16. The scope of this method is limited to those congeners which are the most water soluble; those isomers with the least chlorine substitution. Irradiation – If a deoxygenated mixture of PCBs in isopropanol or mineral oil is subject to irradiation with gamma rays then the PCBs will be dechlorinated to form inorganic chloride and biphenyl. 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(External Link

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Microbial

Much recent work has centered on the study of micro-organisms that are able to decompose PCBs. Generally, 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. Firstly, 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. Secondly, microbial dechlorination tends to be rather slow acting on PCB as a soil contaminant in comparison to other methods. Finally, while microbes work well in laboratory conditions, there's often a problem in transferring a successful laboratory strain to a natural system. This is because the microbes can access other sources of carbon, which they decompose in preference to PCBs.
Further recent developments have focused on testing enzymes and vitamins extracted from microbes which show PCB activity. Especially promising seems to be the use of vitamin B12, in which a cobalt ion is in oxidation state (III) under normal redox conditions. Using titanium (III) citrate as a strong reductant converts the cobalt from Co(III) to Co(I), giving a new vitamin known as B12s, which is a powerful nucleophile and reducing catalyst. This can then be used on PCBs, which it dechlorinates in a rapid and selective manner.

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're 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, therefore 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.

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