Volatile organic compound
Volatile organic compounds (VOCs) are organic chemicals that have a high vapor pressure at ordinary room temperature. Their high vapor pressure results from a low boiling point, which causes large numbers of molecules to evaporate or sublimate from the liquid or solid form of the compound and enter the surrounding air, a trait known as volatility. For example, formaldehyde, which evaporates from paint and releases from materials like quartz, has a boiling point of only –19 °C (–2 °F).
VOCs are numerous, varied, and ubiquitous. They include both human-made and naturally occurring chemical compounds. Most scents or odors are of VOCs. VOCs play an important role in communication between plants, and messages from plants to animals. Some VOCs are dangerous to human health or cause harm to the environment. Anthropogenic VOCs are regulated by law, especially indoors, where concentrations are the highest. Harmful VOCs typically are not acutely toxic, but have compounding long-term health effects. Because the concentrations are usually low and the symptoms slow to develop, research into VOCs and their effects is difficult.
The definitions of VOCs used for control of precursors of photochemical smog used by the U.S. Environmental Protection Agency (EPA) and state agencies in the US with independent outdoor air pollution regulations include exemptions for VOCs that are determined to be non-reactive, or of low-reactivity in the smog formation process.
In the US, regulatory requirements for VOCs vary among the states. Most prominent is the VOC regulation issued by the South Coast Air Quality Management District in California and by the California Air Resources Board (ARB). However, this specific use of the term VOCs can be misleading, especially when applied to indoor air quality because many chemicals that are not regulated as outdoor air pollution can still be important for indoor air pollution.
California's ARB uses the term "reactive organic gases" (ROG) to measure organic gases after public hearing in September 1995. The ARB revised the definition of "Volatile Organic Compounds" used in the consumer products regulations, based on their committee's findings.
Health Canada classifies VOCs as organic compounds that have boiling points roughly in the range of 50 to 250 °C (122 to 482 °F). The emphasis is placed on commonly encountered VOCs that would have an effect on air quality.
The European Union defines a VOC as "any organic compound having an initial boiling point less than or equal to 250 °C (482 °F) measured at a standard atmospheric pressure of 101.3 kPa." The VOC Solvents Emissions Directive is the main policy instrument for the reduction of industrial emissions of volatile organic compounds (VOCs) in the European Union. It covers a wide range of solvent using activities, e.g. printing, surface cleaning, vehicle coating, dry cleaning and manufacture of footwear and pharmaceutical products. The VOC Solvents Emissions Directive requires installations in which such activities are applied to comply either with the emission limit values set out in the Directive or with the requirements of the so-called reduction scheme. Article 13 of The Paints Directive, approved in 2004, amended the original VOC Solvents Emissions Directive and limits the use of organic solvents in decorative paints and varnishes and in vehicle finishing products. The Paints Directive sets out maximum VOC content limit values for paints and varnishes in certain applications.
VOCs (or specific subsets of the VOCs) are legally defined in the various laws and codes under which they are regulated. Other definitions may be found from government agencies investigating or advising about VOCs. EPA regulates VOCs in the air, water, and land. The federal regulations issued under the Safe Drinking Water Act set maximum contaminant level standards for several organic compounds in public water systems. EPA also publishes wastewater testing methods for chemical compounds, including a range of VOCs, pursuant to the Clean Water Act.
In addition to drinking water, VOCs are regulated in pollutant discharges to surface waters (both directly and via sewage treatment plants), as hazardous waste, but not in non-industrial indoor air. The Occupational Safety and Health Administration (OSHA) regulates VOC exposure in the workplace. Volatile organic compounds that are classified as hazardous materials are regulated by the Pipeline and Hazardous Materials Safety Administration while being transported.
Biologically generated VOCs
Not counting methane, biological sources emit an estimated 1150 teragrams of carbon per year in the form of VOCs. The majority of VOCs are produced by plants, the main compound being isoprene. The remainder are produced by animals and microbes. Microbial volatile organic compounds (mVOCs) can also be beneficial, when used to control plant pathogens, for instance.
The strong odor emitted by many plants consists of green leaf volatiles, a subset of VOCs. Emissions are affected by a variety of factors, such as temperature, which determines rates of volatilization and growth, and sunlight, which determines rates of biosynthesis. Emission occurs almost exclusively from the leaves, the stomata in particular. A major class of VOCs is terpenes, such as myrcene. Providing a sense of scale, a forest 62,000 km2 in area (the US state of Pennsylvania) is estimated to emit 3,400,000 kilograms of terpenes on a typical August day during the growing season. VOCs should be a factor in choosing which trees to plant in urban areas. Induction of genes producing volatile organic compounds, and subsequent increase in volatile terpenes has been achieved in maize using (Z)-3-Hexen-1-ol and other plant hormones.
Paints and coatings
A major source of man-made VOCs are coatings, especially paints and protective coatings. Solvents are required to spread a protective or decorative film. Approximately 12 billion litres of paints are produced annually. Typical solvents are aliphatic hydrocarbons, ethyl acetate, glycol ethers, and acetone. Motivated by cost, environmental concerns, and regulation, the paint and coating industries are increasingly shifting toward aqueous solvents.
Chlorofluorocarbons and chlorocarbons
Chlorofluorocarbons, which are banned or highly regulated, were widely used cleaning products and refrigerants. Tetrachloroethene is used widely in dry cleaning and by industry.
One VOC that is a known human carcinogen is benzene, which is a chemical found in environmental tobacco smoke, stored fuels, and exhaust from cars. Benzene also has natural sources such as volcanoes and forest fires. It is frequently used to make other chemicals in the production of plastics, resins, and synthetic fibers. Benzene evaporates into the air quickly and the vapor of benzene is heavier than air allowing the compound to sink into low-lying areas. Benzene has also been known to contaminate food and water and if digested can lead to vomiting, dizziness, sleepiness, rapid heartbeat, and at high levels, even death may occur.
Methylene chloride can be found in adhesive removers and aerosol spray paints. In the human body, methylene chloride is metabolized to carbon monoxide. If a product that contains methylene chloride needs to be used the best way to protect human health is to use the product outdoors. If it must be used indoors, proper ventilation will help to keep exposure levels down. In the United States, methylene chloride is listed as exempt from VOC status.
Perchloroethylene is a volatile organic compound that has been linked to causing cancer in animals. It is also suspected to cause many of the breathing related symptoms of exposure to VOCs. Perchloroethylene is used mostly in dry cleaning. While dry cleaners recapture perchloroethylene in the dry cleaning process to reuse it, some environmental release is unavoidable.
MTBE was banned in certain states in the US around 2004 in order to limit further contamination of drinking water aquifers (groundwater) primarily from leaking underground gasoline storage tanks where MTBE was used as an octane booster and oxygenated-additive.
Many building materials such as paints, adhesives, wall boards, and ceiling tiles slowly emit formaldehyde, which irritates the mucous membranes and can make a person irritated and uncomfortable. Formaldehyde emissions from wood are in the range of 0.02–0.04 ppm. Relative humidity within an indoor environment can also affect the emissions of formaldehyde. High relative humidity and high temperatures allow more vaporization of formaldehyde from wood-materials.
Since many people spend much of their time indoors, long-term exposure to VOCs in the indoor environment can contribute to sick building syndrome. In offices, VOC results from new furnishings, wall coverings, and office equipment such as photocopy machines, which can off-gas VOCs into the air. Good ventilation and air-conditioning systems are helpful at reducing VOCs in the indoor environment. Studies also show that relative leukemia and lymphoma can increase through prolonged exposure of VOCs in the indoor environment.
In the United States, there are two standardized methods for measuring VOCs, one by the National Institute for Occupational Safety and Health (NIOSH) and another by OSHA. Each method uses a single component solvent; butanol and hexane cannot be sampled, however, on the same sample matrix using the NIOSH or OSHA method.
The aromatic VOC compound benzene, emitted from exhaled cigarette smoke, is labeled as carcinogenic and is ten times higher in smokers than in nonsmokers.
EPA has found concentrations of VOCs in indoor air to be 2 to 5 times greater than in outdoor air and sometimes far greater. During certain activities indoor levels of VOCs may reach 1,000 times that of the outside air. Studies have shown that individual VOC emissions by themselves are not that high in an indoor environment, but the indoor total VOC (TVOC) concentrations can be up to five times higher than the VOC outdoor levels. New buildings especially, contribute to the highest level of VOC off-gassing in an indoor environment because of the abundant new materials generating VOC particles at the same time in such a short time period. In addition to new buildings, many consumer products emit VOCs, therefore the total concentration of VOC levels is much greater within the indoor environment.
VOC concentration in an indoor environment during winter is three to four times higher than the VOC concentrations during the summer. High indoor VOC levels are attributed to the low rates of air exchange between the indoor and outdoor environment as a result of tight-shut windows and the increasing use of humidifiers.
Indoor air quality measurements
Measurement of VOCs from the indoor air is done with sorption tubes e. g. Tenax® (for VOCs and SVOCs) or DNPH-cartridges (for carbonyl-compounds). The VOCs adsorb on these materials and are afterwards desorbed either thermally (Tenax®) or by elution (DNPH) and then analyzed by GC-MS/FID or HPLC. Reference gas mixtures are required for quality control of these VOC-measurements. Furthermore, VOC emitting products used indoors, e. g. building products and furniture, are investigated in emission test chambers under controlled climatic conditions. For quality control of these measurements round robin tests are carried out, therefore reproducibly emitting reference materials are ideally required.
Regulation of indoor VOC emissions
In most countries, a separate definition of VOCs is used with regard to indoor air quality that comprises each organic chemical compound that can be measured as follows: adsorption from air on Tenax TA, thermal desorption, gas chromatographic separation over a 100% nonpolar column (dimethylpolysiloxane). VOC (volatile organic compounds) are all compounds that appear in the gas chromatogram between and including n-hexane and n-hexadecane. Compounds appearing earlier are called VVOC (very volatile organic compounds); compounds appearing later are called SVOC (semi-volatile organic compounds).
France, Germany, and Belgium have enacted regulations to limit VOC emissions from commercial products, and industry has developed numerous voluntary ecolabels and rating systems, such as EMICODE, M1, Blue Angel and Indoor Air Comfort In the United States, several standards exist; California Standard CDPH Section 01350 is the most common one. These regulations and standards changed the marketplace, leading to an increasing number of low-emitting products.
Some VOCs, such as styrene and limonene, can react with nitrogen oxides or with ozone to produce new oxidation products and secondary aerosols, which can cause sensory irritation symptoms. VOCs contribute to the formation of Tropospheric ozone and smog.
Health effects include eye, nose, and throat irritation; headaches, loss of coordination, nausea; and damage to the liver, kidney, and central nervous system. Some organics can cause cancer in animals; some are suspected or known to cause cancer in humans. Key signs or symptoms associated with exposure to VOCs include conjunctival irritation, nose and throat discomfort, headache, allergic skin reaction, dyspnea, declines in serum cholinesterase levels, nausea, vomiting, nose bleeding, fatigue, dizziness.
The ability of organic chemicals to cause health effects varies greatly from those that are highly toxic, to those with no known health effects. As with other pollutants, the extent and nature of the health effect will depend on many factors including level of exposure and length of time exposed. Eye and respiratory tract irritation, headaches, dizziness, visual disorders, and memory impairment are among the immediate symptoms that some people have experienced soon after exposure to some organics. At present, not much is known about what health effects occur from the levels of organics usually found in homes. Many organic compounds are known to cause cancer in animals; some are suspected of causing, or are known to cause, cancer in humans.
To reduce exposure to these toxins, one should buy products that contain Low-VOCs or No VOCs. Only the quantity which will soon be needed should be purchased, eliminating stockpiling of these chemicals. Use products with VOCs in well ventilated areas. When designing homes and buildings, design teams can implement the best possible ventilation plans, call for the best mechanical systems available, and design assemblies to reduce the amount of infiltration into the building. These methods will help improve indoor air quality, but by themselves they cannot keep a building from becoming an unhealthy place to breathe.
Limit values for VOC emissions
Limit values for VOC emissions into indoor air are published by AgBB, AFSSET, California Department of Public Health, and others. These regulations have prompted several companies in the paint and adhesive industries to adapt with VOC level reductions their products. VOC labels and certification programs may not properly assess all of the VOCs emitted from the product, including some chemical compounds that may be relevant for indoor air quality. Each ounce of colorant added to tint paint may contain between 5 and 20 grams of VOCs. A dark color, however, could require 5-15 ounces of colorant, adding up to 300 or more grams of VOCs per gallon of paint.
The exhaled human breath contains a few thousand volatile organic compounds and is used in breath biopsy to serve as a VOC biomarker to test for diseases such as lung cancer. One study has shown that "volatile organic compounds ... are mainly blood borne and therefore enable monitoring of different processes in the body." And it appears that VOC compounds in the body "may be either produced by metabolic processes or inhaled/absorbed from exogenous sources" such as environmental tobacco smoke. Research is still in the process to determine whether VOCs in the body are contributed by cellular processes or by the cancerous tumors in the lung or other organs.
Principle and measurement methods
VOCs in the environment or certain atmospheres can be detected based on different principles and interactions between the organic compounds and the sensor components. In many cases, VOCs are detectable to the human nose, and odor wheels are sometimes developed to help humans classify complex odors of wine, coffee, and even paper.
There are electronic devices that can detect ppm concentrations despite the non-selectivity. Others can predict with reasonable accuracy the molecular structure of the volatile organic compounds in the environment or enclosed atmospheres and could be used as accurate monitors of the Chemical Fingerprint and further as health monitoring devices.
Solid-phase microextraction (SPME) techniques are used to collect VOCs at low concentrations for analysis.
Direct injection mass spectrometry techniques are frequently utilized for the rapid detection and accurate quantification of VOCs. PTR-MS is among the methods that have been used most extensively for the on-line analysis of biogenic and antropogenic VOCs. Recent PTR-MS instruments based on time-of-flight mass spectrometry have been reported to reach detection limits of 20 pptv after 100 ms and 750 ppqv after 1 min. measurement (signal integration) time. The mass resolution of these devices is between 7000 and 10,500 m/Δm, thus it is possible to separate most common isobaric VOCs and quantify them independently.
Accuracy and traceability
Metrology for VOC measurements
To achieve comparability of VOC measurements, reference standards traceable to SI-units are required. For a number of VOCs gaseous reference standards are available from specialty gas suppliers or national metrology institutes, either in the form of cylinders or dynamic generation methods. However, for many VOCs, such as oxygenated VOCs, monoterpenes, or formaldehyde, no standards are available at the appropriate amount of fraction due to the chemical reactivity or adsorption of these molecules. Currently, several national metrology institutes are working on the lacking standard gas mixtures at trace level concentration, minimising adsorption processes, and improving the zero gas. The final scopes are for the traceability and the long-term stability of the standard gases to be in accordance with the data quality objectives (DQO, maximum uncertainty of 20% in this case) required by the WMO/GAW program.
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