Polybrominated biphenyl
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Polybrominated biphenyls (PBBs), also called brominated biphenyls or polybromobiphenyls, are a group of manufactured chemicals that consist of polyhalogenated derivatives of a
biphenyl Biphenyl (also known as diphenyl, phenylbenzene, 1,1′-biphenyl, lemonene or BP) is an organic compound that forms colorless crystals. Particularly in older literature, compounds containing the functional group consisting of biphenyl less one ...
core. Their chlorine analogs are the PCBs. While once widely used commercially, PBBs are now controlled substances under the
Restriction of Hazardous Substances Directive The Restriction of Hazardous Substances Directive 2002/95/EC (RoHS 1), short for Directive on the restriction of the use of certain hazardous substances in electrical and electronic equipment, was adopted in February 2003 by the European Unio ...
, which limits their use in electrical and electronic products sold in the EU.


Characteristics

PBBs usually exist as colorless to off-white solids. PBBs soften at 72
degrees Celsius The degree Celsius is the unit of temperature on the Celsius scale (originally known as the centigrade scale outside Sweden), one of two temperature scales used in the International System of Units (SI), the other being the Kelvin scale. The d ...
and decompose above 300 degrees Celsius. They have low
vapor pressure Vapor pressure (or vapour pressure in English-speaking countries other than the US; see spelling differences) or equilibrium vapor pressure is defined as the pressure exerted by a vapor in thermodynamic equilibrium with its condensed pha ...
, are very soluble in
benzene Benzene is an organic chemical compound with the molecular formula C6H6. The benzene molecule is composed of six carbon atoms joined in a planar ring with one hydrogen atom attached to each. Because it contains only carbon and hydrogen atoms ...
and
toluene Toluene (), also known as toluol (), is a substituted aromatic hydrocarbon. It is a colorless, water-insoluble liquid with the smell associated with paint thinners. It is a mono-substituted benzene derivative, consisting of a methyl group (CH3) ...
, and insoluble in
water Water (chemical formula ) is an inorganic, transparent, tasteless, odorless, and nearly colorless chemical substance, which is the main constituent of Earth's hydrosphere and the fluids of all known living organisms (in which it acts as ...
. They are degraded by
UV light Ultraviolet (UV) is a form of electromagnetic radiation with wavelength from 10 nm (with a corresponding frequency around 30  PHz) to 400 nm (750  THz), shorter than that of visible light, but longer than X-rays. UV radiation i ...
.


Application

PBBs are used as
flame retardant The term flame retardants subsumes a diverse group of chemicals that are added to manufactured materials, such as plastics and textiles, and surface finishes and coatings. Flame retardants are activated by the presence of an ignition source and ...
s of the
brominated flame retardant Brominated flame retardants (BFRs) are organobromine compounds that have an inhibitory effect on combustion chemistry and tend to reduce the flammability of products containing them. The brominated variety of commercialized chemical flame retardants ...
group. They are added to plastics used in products such as home electrical appliances,
textile Textile is an Hyponymy and hypernymy, umbrella term that includes various Fiber, fiber-based materials, including fibers, yarns, Staple (textiles)#Filament fiber, filaments, Thread (yarn), threads, different #Fabric, fabric types, etc. At f ...
s,
plastic Plastics are a wide range of synthetic or semi-synthetic materials that use polymers as a main ingredient. Their plasticity makes it possible for plastics to be moulded, extruded or pressed into solid objects of various shapes. This adapta ...
foams,
laptop A laptop, laptop computer, or notebook computer is a small, portable personal computer (PC) with a screen and alphanumeric keyboard. Laptops typically have a clam shell form factor with the screen mounted on the inside of the upper li ...
cabinets, etc. to make them difficult to burn. A number of substituted PBBs found application in medicine, namely bromophene and bromofenofos.


Health hazards

Exposure to the coplanar
stereoisomer In stereochemistry, stereoisomerism, or spatial isomerism, is a form of isomerism in which molecules have the same molecular formula and sequence of bonded atoms (constitution), but differ in the three-dimensional orientations of their atoms in ...
3,3',4,4',5,5'-hexabromobiphenyl (but not the non-coplanar stereoisomer) in genetically susceptible mice is known to cause immunotoxicity and disorders related to the central nervous system, and even at doses as low as 2.5 mg/kg, excess neonatal fatalities are observed ( LD50 is from 5–10 mg/kg). The mechanism of toxicity is cellular oxidative stress by aryl hydrocarbon receptor activation. There is evidence that pre- and post-natal exposure to PBB in girls leads to
menarche Menarche ( ; ) is the first menstrual cycle, or first menstrual bleeding, in female humans. From both social and medical perspectives, it is often considered the central event of female puberty, as it signals the possibility of fertility. Gir ...
at an earlier age. Early studies on the effects of PBBs on
human being Humans (''Homo sapiens'') are the most abundant and widespread species of primate, characterized by bipedality, bipedalism and exceptional cognitive skills due to a large and complex Human brain, brain. This has enabled the development of ad ...
s concerned the people in
Michigan Michigan () is a state in the Great Lakes region of the upper Midwestern United States. With a population of nearly 10.12 million and an area of nearly , Michigan is the 10th-largest state by population, the 11th-largest by area, and t ...
, United States who consumed PBB-contaminated animal products (see history of PBBs below). A study of 327 girls aged 5–24 years in Michigan found those who were exposed ''in utero'' to PBBs at or above a level of 7  ppb found had an earlier age at menarche compared to a case-control group. Michigan dairy farmers exposed to PBBs had significant immune system abnormalities including reduced numbers of circulating blood lymphocytes, increases in lymphocytes with no detectable surface markers, and reduced functional response to specific test antigens. Some residents complained of
nausea Nausea is a diffuse sensation of unease and discomfort, sometimes perceived as an urge to vomit. While not painful, it can be a debilitating symptom if prolonged and has been described as placing discomfort on the chest, abdomen, or back of th ...
,
abdominal pain Abdominal pain, also known as a stomach ache, is a symptom associated with both non-serious and serious medical issues. Common causes of pain in the abdomen include gastroenteritis and irritable bowel syndrome. About 15% of people have a m ...
,
loss of appetite Anorexia is a medical term for a loss of appetite. While the term in non-scientific publications is often used interchangeably with anorexia nervosa, many possible causes exist for a loss of appetite, some of which may be harmless, while others i ...
,
joint pain Arthralgia (from Greek ''arthro-'', joint + ''-algos'', pain) literally means ''joint pain''. Specifically, arthralgia is a symptom of injury, infection, illness (in particular arthritis), or an allergic reaction to medication. According to MeSH, ...
and
lethargy Lethargy is a state of tiredness, sleepiness, weariness, fatigue, sluggishness or lack of energy. It can be accompanied by depression, decreased motivation, or apathy. Lethargy can be a normal response to inadequate sleep, overexertion, overwo ...
, though it could not be clearly established that PBBs were the cause of these health problems. Workers who were exposed to PBB during PBB production suffered
hypothyroidism Hypothyroidism (also called ''underactive thyroid'', ''low thyroid'' or ''hypothyreosis'') is a disorder of the endocrine system in which the thyroid gland does not produce enough thyroid hormone. It can cause a number of symptoms, such as ...
, although no deterioration in memory performance was found in PBB-exposed workers in tests conducted several years after final PBB exposure, and there was also no correlation of performance with PBB concentration. There is stronger evidence that PBBs may have caused skin problems, such as
acne Acne, also known as ''acne vulgaris'', is a long-term skin condition that occurs when dead skin cells and oil from the skin clog hair follicles. Typical features of the condition include blackheads or whiteheads, pimples, oily skin, and ...
, in consumers of the contaminated food. Some workers exposed to PBBs by breathing and skin contact for days to months also developed acne. Studies in animals exposed to large amounts of PBBs for a short period or to smaller amounts over a longer period show that PBBs can cause
weight loss Weight loss, in the context of medicine, health, or physical fitness, refers to a reduction of the total body mass, by a mean loss of fluid, body fat ( adipose tissue), or lean mass (namely bone mineral deposits, muscle, tendon, and other co ...
,
skin disorder A skin condition, also known as cutaneous condition, is any medical condition that affects the integumentary system—the organ system that encloses the body and includes skin, nails, and related muscle and glands. The major function of this sy ...
s, nervous and
immune system The immune system is a network of biological processes that protects an organism from diseases. It detects and responds to a wide variety of pathogens, from viruses to parasitic worms, as well as cancer cells and objects such as wood splinte ...
s effects, as well as effects on the
liver The liver is a major organ only found in vertebrates which performs many essential biological functions such as detoxification of the organism, and the synthesis of proteins and biochemicals necessary for digestion and growth. In humans, it i ...
,
kidney The kidneys are two reddish-brown bean-shaped organs found in vertebrates. They are located on the left and right in the retroperitoneal space, and in adult humans are about in length. They receive blood from the paired renal arteries; blo ...
s, and
thyroid gland The thyroid, or thyroid gland, is an endocrine gland in vertebrates. In humans it is in the neck and consists of two connected lobes. The lower two thirds of the lobes are connected by a thin band of tissue called the thyroid isthmus. The thy ...
.


Possibility of carcinogenicity

It is not known for certain if PBBs could cause
cancer Cancer is a group of diseases involving abnormal cell growth with the potential to invade or spread to other parts of the body. These contrast with benign tumors, which do not spread. Possible signs and symptoms include a lump, abnormal b ...
in human beings, but it has been observed that they can lead to cancer in lab mice exposed to very high concentrations of PBBs. Based on such animal tests, the
United States Department of Health and Human Services The United States Department of Health and Human Services (HHS) is a cabinet-level executive branch department of the U.S. federal government created to protect the health of all Americans and providing essential human services. Its motto is ...
has determined that PBBs may reasonably be anticipated to be
carcinogen A carcinogen is any substance, radionuclide, or radiation that promotes carcinogenesis (the formation of cancer). This may be due to the ability to damage the genome or to the disruption of cellular metabolic processes. Several radioactive sub ...
s. The
International Agency for Research on Cancer The International Agency for Research on Cancer (IARC; french: Centre International de Recherche sur le Cancer, CIRC) is an intergovernmental agency forming part of the World Health Organization of the United Nations. Its role is to conduct and ...
also suggests that PBBs are possibly carcinogenic to humans.


Michigan PBB contamination incident

Before the 1970s, PBBs were widely used commercially as a
flame retardant The term flame retardants subsumes a diverse group of chemicals that are added to manufactured materials, such as plastics and textiles, and surface finishes and coatings. Flame retardants are activated by the presence of an ignition source and ...
. Michigan Chemical Corporation (MCC) in
St. Louis, Michigan St. Louis is a city in Gratiot County in the U.S. state of Michigan. As of the 2010 census the population was 7,482. Geography According to the United States Census Bureau, the city has a total area of , of which is land and is water. It was ...
, which was then owned by Velsicol Chemical Corporation, was a major producer of the FireMaster range of PBB-based flame retardants. FireMaster BP-6 (a yellow-brown powder) is a mixture of many different PBB congeners with 2,2',4,4',5,5'-hexabromobiphenyl and 2,2',3,4,4',5,5'-heptabromobiphenyl being significant constituents by mass (60-80% and 12-25%, respectively).US ATSDR (2004) FireMaster FF-1 (a white powder) is FireMaster BP-6 with the addition of 2% calcium silicate as an anti-caking agent. Mixed bromochlorobiphenyls and polybrominated naphthalenes, as well as lower brominated compounds formed by incomplete bromination, have also been found as minor constituents of FireMaster products. In summer 1973, several thousand pounds of FireMaster BP-6 were accidentally mixed with livestock feed that was distributed to farms in
Michigan Michigan () is a state in the Great Lakes region of the upper Midwestern United States. With a population of nearly 10.12 million and an area of nearly , Michigan is the 10th-largest state by population, the 11th-largest by area, and t ...
, United States because the MCC plant also produced a feed pre-cursor ingredient,
magnesium oxide Magnesium oxide ( Mg O), or magnesia, is a white hygroscopic solid mineral that occurs naturally as periclase and is a source of magnesium (see also oxide). It has an empirical formula of MgO and consists of a lattice of Mg2+ ions and O2∠...
, which was sold to the feed manufacturer. Some 1.5 million
chicken The chicken (''Gallus gallus domesticus'') is a domesticated junglefowl species, with attributes of wild species such as the grey and the Ceylon junglefowl that are originally from Southeastern Asia. Rooster or cock is a term for an adu ...
s, 30,000
cattle Cattle (''Bos taurus'') are large, domesticated, cloven-hooved, herbivores. They are a prominent modern member of the subfamily Bovinae and the most widespread species of the genus '' Bos''. Adult females are referred to as cows and adult ...
, 5,900 pigs, and 1,470
sheep Sheep or domestic sheep (''Ovis aries'') are domesticated, ruminant mammals typically kept as livestock. Although the term ''sheep'' can apply to other species in the genus '' Ovis'', in everyday usage it almost always refers to domesticate ...
then consumed this feed, became contaminated with PBBs and the carcasses were disposed of in landfill sites throughout the state. In 1976, the Michigan Department of Community Health established a PBB registry to gather and analyze data on exposed residents. It now resides at the
Rollins School of Public Health The Rollins School of Public Health (RSPH) is the public health school of Emory University. Founded in 1990, Rollins has more than 1,100 students pursuing master's degrees ( MPH/MSPH) and over 150 students pursuing doctorate degrees ( PhD). Th ...
at
Emory University Emory University is a private research university in Atlanta, Georgia. Founded in 1836 as "Emory College" by the Methodist Episcopal Church and named in honor of Methodist bishop John Emory, Emory is the second-oldest private institution of ...
, and is maintained by epidemiologist Michele Marcus. Michigan Farmer magazine staff members Richard Lehnert and Bonnie Pollard broke the news of the contamination. The magazine continued coverage of the issue until the eventual bankruptcy proceedings of the farm cooperative responsible for the accidental contamination and subsequent distribution of the feed.David Weinstock, Michigan Farmer managing editor, 1988-1991 These events were also portrayed in the 1981 documentary ''Cattlegate'' by Jeff Jackson, the true-fiction film '' Bitter Harvest'' starring
Ron Howard Ronald William Howard (born March 1, 1954) is an American director, producer, screenwriter, and actor. He first came to prominence as a child actor, guest-starring in several television series, including an episode of '' The Twilight Zone''. ...
, and in the book ''The Poisoning of Michigan'' by Joyce Egginton. A 1978 episode of '' Lou Grant'' ("Slaughter") portrays a similar, but fictionalized account. One year elapsed before the animals were culled. This incident is cited amongst a handful of other noxious substances as the driver for
Gerald Ford Gerald Rudolph Ford Jr. ( ; born Leslie Lynch King Jr.; July 14, 1913December 26, 2006) was an American politician who served as the 38th president of the United States from 1974 to 1977. He was the only president never to have been elected ...
's half-hearted approval in 1976 of the
Toxic Substances Control Act The Toxic Substances Control Act (TSCA) is a United States law, passed by the 94th United States Congress in 1976 and administered by the United States Environmental Protection Agency (EPA), that regulates chemicals not regulated by other U. ...
, which "remains one of the most controversial regulatory bills ever passed".


Landrigan study

A study was undertaken on 4,545 people to determine the effects of PBBs on
human being Humans (''Homo sapiens'') are the most abundant and widespread species of primate, characterized by bipedality, bipedalism and exceptional cognitive skills due to a large and complex Human brain, brain. This has enabled the development of ad ...
s. These include three exposure groups – all people who lived on the quarantined farms, people who received food from these farms and workers (and their families) engaged in PBB manufacture – as well as 725 people with low-level PBB exposure. All were queried concerning 17 symptoms and conditions possibly related to PBBs.
Venous blood Venous blood is deoxygenated blood which travels from the peripheral blood vessels, through the venous system into the right atrium of the heart. Deoxygenated blood is then pumped by the right ventricle to the lungs via the pulmonary artery wh ...
was drawn and analyzed for PBB by
gas chromatography Gas chromatography (GC) is a common type of chromatography used in analytical chemistry for separating and analyzing compounds that can be vaporized without decomposition. Typical uses of GC include testing the purity of a particular substanc ...
. Mean
serum Serum may refer to: * Serum (blood), plasma from which the clotting proteins have been removed **Antiserum, blood serum with specific antibodies for passive immunity * Serous fluid, any clear bodily fluid *Truth serum, a drug that is likely to mak ...
PBB levels were found to be 26.9 ppb by weight (26.9 Âµg/kg) in farm residents, 17.1 in recipients, 43.0 ppb in workers, and 3.4 ppb in the low exposure group. No associations could be established between serum PBB levels and symptom prevalence rates. To evaluate peripheral
lymphocyte A lymphocyte is a type of white blood cell (leukocyte) in the immune system of most vertebrates. Lymphocytes include natural killer cells (which function in cell-mediated, cytotoxic innate immunity), T cells (for cell-mediated, cytotoxic a ...
function, T and
B cell B cells, also known as B lymphocytes, are a type of white blood cell of the lymphocyte subtype. They function in the humoral immunity component of the adaptive immune system. B cells produce antibody molecules which may be either secreted o ...
quantitation and
in vitro ''In vitro'' (meaning in glass, or ''in the glass'') studies are performed with microorganisms, cells, or biological molecules outside their normal biological context. Colloquially called " test-tube experiments", these studies in biology a ...
responses to three nonspecific mitogens were studied in 34 persons with highest PBB levels (mean: 787 ppb), and in 56 with low levels (mean: 2.8 ppb). No statistically significant differences in lymphocyte function were noted. However, as of 2015 these studies are still ongoing, and 40 years later adverse reproductive-system effects (as measured by the
Apgar score The Apgar score is a quick way for doctors to evaluate the health of all newborns at 1 and 5 minutes after birth and in response to resuscitation. It was originally developed in 1952 by an anesthesiologist at Columbia University, Virginia Apgar ...
of the newborns) continue to be found in the grandchildren of those who consumed tainted farm products.


Bans and restrictions

Noting the possible hazards on the environment, however, PBBs were listed as one of six controlled substances under the
Restriction of Hazardous Substances Directive The Restriction of Hazardous Substances Directive 2002/95/EC (RoHS 1), short for Directive on the restriction of the use of certain hazardous substances in electrical and electronic equipment, was adopted in February 2003 by the European Unio ...
(RoHS), which was enacted into
European Law European Union law is a system of rules operating within the member states of the European Union (EU). Since the founding of the European Coal and Steel Community following World War II, the EU has developed the aim to "promote peace, its valu ...
in February 2003. RoHS legislation lists PBBs as a "restricted substance" group. Other countries followed suit, resulting most recently in restriction dates instituted in China on March 1, 2007 and South Korea on July 1, 2007.


References


External links


Aftermath of Michigan Contamination
{{Aryl hydrocarbon receptor modulators Endocrine disruptors Flame retardants Bromoarenes Persistent organic pollutants under the Stockholm Convention Persistent organic pollutants under the Convention on Long-Range Transboundary Air Pollution Biphenyls 1973 disasters in the United States 1973 in the environment Presidency of Gerald Ford