Dioxins

1. What are dioxins?

• 1.1 What are dioxins chemically?
• 1.2 How are dioxins formed?
• 1.3 What happens to dioxins when they enter the environment?

1.1 What are dioxins chemically?

The source document for this Digest states:

CDDs are a family of 75 different compounds commonly referred to as polychlorinated dioxins. These compounds have varying harmful effects. The CDD family is divided into eight groups of chemicals based on the number of chlorine atoms in the compound. The group with one chlorine atom is called the mono-chlorinated dioxin(s). The groups with two through eight chlorine atoms are called di-chlorinated dioxin (DCDD), tri-chlorinated dioxin (TrCDD), tetra-chlorinated dioxin (TCDD), penta-chlorinated dioxin (PeCDD), hexa-chlorinated dioxin (HxCDD), hepta-chlorinated dioxin (HpCDD), and octa-chlorinated dioxin (OCDD). The chlorine atoms can be attached to the dioxin molecule at any one of eight positions. The name of each CDD indicates both the number and the positions of the chlorine atoms. For example, the CDD with four chlorine atoms at positions 2, 3, 7, and 8 on the dioxin molecule is called 2,3,7,8-tetrachlorodibenzo-p-dioxin or 2,3,7,8-TCDD. 2,3,7,8-TCDD is one of the most toxic of the CDDs to mammals and has received the most attention. Thus, 2,3,7,8-TCDD serves as a prototype for the CDDs. CDDs with toxic properties similar to 2,3,7,8-TCDD are called "dioxin-like" compounds.

In the pure form, CDDs are colorless solids or crystals. CDDs enter the environment as mixtures containing a variety of individual components and impurities. In the environment they tend to be associated with ash, soil, or any surface with a high organic content, such as plant leaves. In air and water, a portion of the CDDs may be found in the vapor or dissolved state, depending on the amount of particulate matter, temperature, and other environmental factors. 2,3,7,8-TCDD is odorless. The odors of the other CDDs are not known.

Source & ©: ATSDR "Public Health Statement for Chlorinated Dibenzo-p-dioxins (CDDs) ", section 1.1

1.2 How are dioxins formed?

The source document for this Digest states:

CDDs are known to occur naturally, and are also produced by human activities. They are naturally produced from the incomplete combustion of organic material by forest fires or volcanic activity. CDDs are not intentionally manufactured by industry, except in small amounts for research purposes. They are unintentionally produced by industrial, municipal, and domestic incineration and combustion processes. Currently, it is believed that CDD emissions associated with human incineration and combustion activities are the predominant environmental source.

CDDs (mainly 2,3,7,8-TCDD) may be formed during the chlorine bleaching process used by pulp and paper mills. CDDs occur as a contaminant in the manufacturing process of certain chlorinated organic chemicals, such as chlorinated phenols. 2,3,7,8-TCDD is a by-product formed during the manufacture of 2,4,5-trichlorophenol (2,4,5-TCP). 2,4,5-TCP was used to produce hexachlorophene (used to kill bacteria) and the herbicide, 2,4,5-trichlorophenoxyacetic acid (2,4,5-T). Various formulations of 2,4,5-T have been used extensively for weed control on crops and range lands, and along roadways throughout the world. 2,4,5-T was a component of Agent Orange, which was used extensively by the U.S. military in the Vietnam War. In most industrialized countries the use of products contaminated with CDDs has been greatly reduced. Use of hexachlorophene and the herbicide 2,4,5-T is currently restricted in the United States. Other chlorinated chemicals, like pentachlorophenol (PCP), used to preserve wood, do contain some of the more highly chlorinated CDDs (those with more chlorine atoms), but 2,3,7,8-TCDD is not usually found. The use of PCP has been restricted to certain manufacturing applications. Currently, CDDs are primarily released to the environment during combustion of fossil fuels (coal, oil, and natural gas) and wood, and during incineration processes (municipal and medical solid waste and hazardous waste incineration). While incineration may be the primary current source of release of CDDs into the environment, the levels of CDDs produced by incineration are extremely low. CDDs are associated with ash generated in combustion and incineration processes. Emissions from incinerator sources vary greatly and depend on management practices and applied technologies. CDDs also have been detected at low concentrations in cigarette smoke, home-heating systems, and exhaust from cars running on leaded gasoline or unleaded gasoline, and diesel fuel. Burning of many materials that may contain chlorine, such as plastics, wood treated with pentachlorophenol (PCP), pesticide-treated wastes, other polychlorinated chemicals (polychlorinated biphenyls or PCBs), and even bleached paper can produce CDDs.

Although this public health statement will focus on CDDs, it is important to note that CDDs are found in the environment together with other structurally related chlorinated chemicals, such as chlorinated dibenzofurans (CDFs) and polychlorinated biphenyls (PCBs). Therefore, people are generally exposed to mixtures of CDDs and other classes of toxicologically and structurally similar compounds. 2,3,7,8-TCDD is one of the most toxic and extensively studied of the CDDs and serves as a prototype for the toxicologically relevant or "dioxin-like" CDDs. Based on results from animal studies, scientists have learned that they can express the toxicity of dioxin-like CDDs as a fraction of the toxicity attributed to 2,3,7,8-TCDD. For example, the toxicity of dioxin-like CDDs can be half or one tenth or any fraction of that of 2,3,7,8-TCDD. Scientists call that fraction a Toxic Equivalent Factor (TEF).

Source & ©: ATSDR "Public Health Statement for Chlorinated Dibenzo-p-dioxins (CDDs) ", section 1.1

1.3 What happens to dioxins when they enter the environment?

The source document for this Digest states:

CDDs are released into the air in emissions from municipal solid waste and industrial incinerators. Exhaust from vehicles powered with leaded and unleaded gasoline and diesel fuel also release CDDs to the air. Other sources of CDDs in air include: emissions from oil- or coal-fired power plants, burning of chlorinated compounds such as PCBs, and cigarette smoke. CDDs formed during combustion processes are associated with small particles in the air, such as ash. The larger particles will be deposited close to the emission source, while very small particles may be transported longer distances. Some of the lower chlorinated CDDs (DCDD, TrCDD, and some of the TCDDs) may vaporize from the particles (and soil or water surfaces) and be transported long distances in the atmosphere, even around the globe. It has been estimated that 20 to 60% of 2,3,7,8-TCDD in the air is in the vapor phase. Sunlight and atmospheric chemicals will break down a very small portion of the CDDs, but most CDDs will be deposited on land or water.

CDDs occur as a contaminant in the manufacture of various chlorinated pesticides and herbicides, and releases to the environment have occurred during the use of these chemicals. Because CDDs remain in the environment for a long time, contamination from past pesticide and herbicide use may still be of concern. In addition, improper storage or disposal of these pesticides and waste generated during their production can lead to CDD contamination of soil and water.

CDDs are released in waste waters from pulp and paper mills that use chlorine or chlorine-containing chemicals in the bleaching process. Some of the CDDs deposited on or near the water surface will be broken down by sunlight. A very small portion of the total CDDs in water will evaporate to air. Because CDDs do not dissolve easily in water, most of the CDDs in water will attach strongly to small particles of soil or organic matter and eventually settle to the bottom. CDDs may also attach to microscopic plants and animals (plankton) which are eaten by larger animals, that are in turn eaten by even larger animals. This is called a food chain. Concentrations of chemicals such as the most toxic, 2,3,7,8-chlorine substituted CDDs, which are difficult for the animals to break down, usually increase at each step in the food chain. This process, called biomagnification, is the reason why undetectable levels of CDDs in water can result in measurable concentrations in aquatic animals. The food chain is the main route by which CDD concentrations build up in larger fish, although some fish may accumulate CDDs by eating particles containing CDDs directly off the bottom.

CDDs deposited on land from combustion sources or from herbicide or pesticide applications bind strongly to the soil, and therefore are not likely to contaminate groundwater by moving deeper into the soil. However, the presence of other chemical pollutants in contaminated soils, such as those found at hazardous waste sites or associated with chemical spills (for example, oil spills), may dissolve CDDs, making it easier for CDDs to move through the soil. The movement of chemical waste containing CDDs through soil has resulted in contamination of groundwater. Soil erosion and surface runoff can also transport CDDs into surface waters. A very small amount of CDDs at the soil surface will evaporate into air. Certain types of soil bacteria and fungus can break CDDs down, but the process is very slow. In fact, CDDs can exist in soil for many years. Plants take up only very small amounts of CDDs by their roots. Most of the CDDs found on the parts of plants above the ground probably come from air and dust and/or previous use of CDD-containing pesticides or herbicides. Animals (such as cattle) feeding on the plants may accumulate CDDs in their body tissues (meat) and milk.

Source & ©: ATSDR "Public Health Statement for Chlorinated Dibenzo-p-dioxins (CDDs) ", section 1.2