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Dioxins and dioxin-like compounds

Dioxins and dioxin-like compounds (DLCs) are a group of chemical compounds that are persistent organic pollutants (POPs) in the environment. They are mostly by-products of burning or various industrial processes or, in the case of dioxin-like PCBs and PBBs, unwanted minor components of intentionally produced mixtures.

Chemistry
There are 75 possible congeners of polychlorinated dibenzo-p-dioxins, but only 7 of them have affinity for the aryl hydrocarbon receptor (AH receptor) and are toxic via this mechanism. The crucial structures are so called lateral chlorines in positions 2,3,7, and 8. These 4 chlorines also make the congeners persistent, because they prevent microbial degradation. Additional chlorines make the compounds less potent, but basically the effects remain the same although at higher doses. There are 135 possible dibenzofurans, and 10 in which the lateral chlorines are dioxin-like. ==Mechanism of action==
Mechanism of action
The aryl hydrocarbon receptor (AH receptor) is an ancient receptor, and its many functions have been revealed only recently. It is an over 600-million-year-old protein occurring in all vertebrates, and its homologs have been discovered in invertebrates and insects. It is classified as a member of the basic helix-loop-helix/Per-Arnt-Sim (bHLH/PAS) family of transcription factors, and it acts to modify transcription of a number of genes (see figure). AH receptor activity is necessary for normal development and many physiological functions. Mice lacking the AH receptor (knockouts) are sick with cardiac hypertrophy, liver fibrosis, reproductive problems, and impaired immunology. This is in essence a protective function preventing toxic or carcinogenic effects of xenobiotics, but in some conditions it may also result in the production of reactive metabolites that are mutagenic and carcinogenic. This enzyme induction can be initiated by many natural or synthetic compounds, e.g., carcinogenic polycyclic hydrocarbons such as benzo(a)pyrene, Binding of dioxin-like compounds to the AH receptor has made it possible to measure total dioxin-like activity of a sample using CALUX (Chemical Activated LUciferase gene eXpression) bioassay. The results have been comparable to TEQ levels measured by much more expensive gas chromatography-high resolution mass spectrometry in environmental samples. ==Toxicity==
Toxicity
Dioxin toxicity is based on inappropriate activation of a physiologically important receptor, and therefore dose-response must be carefully considered. The endocrine disrupting activity of dioxins is thought to occur as a down-stream function of AH receptor activation, with thyroid status in particular being a sensitive marker of exposure. TCDD, along with the other PCDDs, PCDFs and dioxin-like coplanar PCBs are not direct agonists or antagonists of hormones, and are not active in assays which directly screen for these activities such as ER-CALUX and AR-CALUX. These compounds have also not been shown to have any direct mutagenic or genotoxic activity. Their main action in causing cancer is cancer promotion. A mixture of PCBs such as Aroclor may contain PCB compounds which are known estrogen agonists but are not classified as dioxin-like in terms of toxicity. Mutagenic effects have been established for some lower chlorinated chemicals such as 3-chlorodibenzofuran, which is neither persistent nor an AH receptor agonist. Toxicity in animals High doses. The symptoms reported to be associated with dioxin toxicity in animal studies are incredibly wide-ranging, both in the scope of the biological systems affected and in the range of dosage needed to bring these about. Well established developmental effects are cleft palate, hydronephrosis, disturbances in tooth development and sexual development, and endocrine effects. Three women in Vienna, Austria, were poisoned with large doses of TCDD in 1998. The highest concentration of TCDD in fat tissue was 144,000 pg/g, the highest ever reported in human beings. The main feature was chloracne, a serious skin disease. The victim survived, and other symptoms were modest after initial gastrointestinal symptoms and amenorrhea. Another acute incident was the deliberate poisoning of Victor Yushchenko, then presidential candidate of Ukraine, in 2004. TCDD concentration in fat was 108,000 pg/g. In this case, the most prominent symptoms were chloracne, hepatitis and pancreatitis. The deliberate poisoning case shows that a human being is not as sensitive as other animals, since Yushchenko survived a dose estimated at around 25 μg/kg. Two serious food contamination accidents were caused by PCB oils used in heat exchangers. Perhaps the best known dioxin accident occurred in Seveso, Italy, in 1976. A tank of chlorophenols released its contents to air including many kilograms of TCDD, and contaminated much of the city. The highest TCDD levels were found in children, up to 56,000 pg/g fat. Acute effects were limited to chloracne, although many animals such as rabbits died after eating contaminated grass. Dental aberrations were found after 25 years in persons exposed as children, and a slightly increased cancer risk was confirmed 35 years later. and of sexual development. An example of the variation in responses is clearly seen in a study following the Seveso disaster indicating that sperm count and motility were affected in different ways in exposed males, depending on whether they were exposed before, during or after puberty. In occupational settings many symptoms have been seen, but exposures have always been to a multitude of chemicals including chlorophenols, chlorophenoxy acid herbicides, and solvents. Therefore, definitive proof of dioxins as causative factors has been difficult to obtain. By far the best proven effect is chloracne. The suspected effects in adults are liver damage, and alterations in heme metabolism, serum lipid levels, thyroid functions, as well as diabetes and immunological effects. or at least 1000 times lower than those in poisonings (see above). Tooth deformities have been considered plausible after long breast-feeding, when the dioxin concentrations were high in 1970s and 1980s. When the concentrations decreased during 1990s and 2000s, the effects were no longer seen. This was in industrial environments causing relatively high exposures to boys as well as their mothers. This recommendation can be challenged, because it does not properly consider competing risks following from lost benefits of important and healthy food items such as certain fish. A general conclusion may be that safety margins are not very great concerning developmental effects, but toxic effects are not likely at the present population levels of dioxins. A number of cross-sectional studies have shown associations between type 2 diabetes and several POP compounds including dioxins. Such observational studies cannot prove causality, i.e. there may be an association which does not prove that one is the cause of the other. The main problem is that similar associations can be found with many quite different POPs, which have only long half-lives and tendency to accumulate in lipids in common. This suggests that they may all be related to diet and obesity which are by far the most common causes of type 2 diabetes. is insignificant compared with daily dioxin intake from food. The United States Environmental Protection Agency has categorised dioxin, and the mixture of substances associated with sources of dioxin toxicity as a "likely human carcinogen". The International Agency for Research on Cancer has classified TCDD as a human carcinogen (class 1) on the basis of clear animal carcinogenicity and limited human data, and subsequently also 2,3,4,7,8-PCDF and PCB 126 as class 1 carcinogens. The mechanism is thought to be mainly promotion, i.e. dioxins can accelerate the formation of tumours caused by other factors, and adversely affect the normal mechanisms for inhibiting tumour growth. As with many toxic endpoints of dioxin, a clear dose–response relationship is difficult to establish. After accidental or high occupational exposures there is evidence on human carcinogenicity. Increases in cancer have been modest, in fact reaching statistical significance has been difficult even after high accidental or occupational exposures like in Yusho and Yucheng poisonings, Seveso accident, and combined occupational cohorts. All this means that in case of important beneficial food items and breast feeding a thorough benefit/risk analysis is needed before setting limits, in order to avoid increased other risks or lost benefits. Risk assessment The uncertainty and variability in the dose–response relationship of dioxins in terms of their toxicity, as well as the ability of dioxins to bioaccumulate, have led WHO experts to recommending very low tolerable daily intake (TDI) of dioxin, 1-4 pg/kg body weight per day, i.e. 7×10−11 to 2.8×10−10g per 70-kg person per day, to allow for this uncertainty and ensure public safety in all instances. Recently also developmental effects have been reassessed by the Contamination Panel of the European Food Safety Agency (EFSA). They propose decreasing the tolerable weekly intake (TWI) from 14 pg/kg to 2 pg/kg. This resembles the common measure of all alcoholic drinks: beer, wine and whiskey can be added together as absolute alcohol, and this sum gives the toxicologically meaningful measure of the total impact. The TEQ only applies to dioxin-like effects mediated by the AHR. Some toxic effects (especially of PCBs) may be independent of the AHR, and those are not taken into account by using TEQs. TEFs are also approximations with certain amount of scientific judgement rather than scientific facts. Therefore, they may be re-evaluated from time to time. There have been several TEF versions since the 1980s. The most recent re-assessment was by an expert group of the World Health organization in 2005. and substituent numbering scheme of the parent compound dibenzo-p-dioxin :(T = tetra, Pe = penta, Hx = hexa, Hp = hepta, O = octa) File:2,3,7,8-substituted PCDD.svg|The 2,3,7,8-substituted PCDDs Sharon Beder and others have argued that the dioxin controversy has been very political and that large companies have tried to play down the seriousness of the problems of dioxin. The companies involved have often said that the campaign against dioxin is based on "fear and emotion" and not on science. ==Human intake and levels==
Human intake and levels
Most intake of dioxin-like chemicals is from food of animal origin: meat, dairy products, or fish predominate, depending on the country. The daily intake of dioxins and dioxin-like PCBs as TEQ is of the order of 100 pg/day, i.e. 1-2 pg/kg/day. For the same reason, short term higher intake such as after food contamination incidents, is not crucial unless it is extremely high or lasts for several months or years. and the trends have been similar in the U.S. The most useful measure of time trends is concentration in breast milk measured over decades. In the U.S. young adult female population (age group 20–39), the concentration was 9.7 pg/g lipid in 2001-2002 (geometric mean). This along with high industrial exposures may be the most valuable source of information on the health risks of dioxins. The same features causing persistence of dioxins in the environment also cause very slow elimination in humans and animals. Because of low water solubility, kidneys cannot excrete them in urine as such. They must first be metabolised to more-water-soluble metabolites, but that metabolism, especially in humans, is extremely slow. This results in biological half-lives of several years for all dioxins. That of TCDD is estimated to be 7 to 8 years, and for other PCDD/Fs from 1.4 to 13 years, PCDFs on average slightly shorter than PCDDs. In mammals, dioxins are found mostly in fat. Concentrations in fat seem to be relatively similar, be it serum fat, adipose tissue fat, or milk fat. This permits measuring dioxin burden by analysing breast milk. Initially, however, at least in laboratory animals, after a single dose, high concentrations are found in the liver, but in a few days, adipose tissue will predominate. In rat liver, however, high doses cause induction of CYP1A2 enzyme, and this binds dioxins. Thus, depending on the dose, the ratio of fat and liver tissue concentrations may vary considerably in rodents. ==Uses==
Uses
Dioxins have no common uses. They are manufactured on a small scale for chemical and toxicological research, but mostly exist as by-products of industrial processes such as chlorine bleaching of paper pulp, pesticide manufacture, and combustion processes such as incineration. The defoliant Agent Orange contained trace amounts of dioxin impurities and caused severe health issues as a result. The wood preservative pentachlorophenol often contained dioxins and dibenzofurans as impurities. The Stockholm Convention banned the production and use of dioxins in 2001. ==Sources==
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