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COLIPA, industry studies find exposure levels well below limits set by EPA.
January 5, 2022
By: Paolo Giacomoni
Consultant
Many of us fear ants because some of them spray an irritating poison that can be fastidious to the skin. In 1671, John Ray distillated crushed ants and isolated a colorless acid with pungent odor. He called it formic acid because the Latin name of ant is formica. Formic acid’s formula is HCOOH. It is the simplest organic acid and is used for animal feed, leather tanning, textile dyeing, rubber products and coating. According to analysts, 15 million metric tons, valued at $1.5 billion, are produced every year. Heating formic acid at 250-400°C in the presence of zinc produces zinc oxide and the aldehyde of formic acid that is, formaldehyde: H2C=O.1 So, formaldehyde itself is somehow related to stinging ants! Formaldehyde in Nature Formaldehyde is present in many fruits, such as apples, bananas, pears and tomatoes. Concentrations vary between 6 and 60mg per kilogram or 6-60ppm. Some mushrooms contain as much as 400ppm of formaldehyde. In the process of oxidizing tetrahydrofolic acid to synthesize amino acids and purines, the body produces and turns over every day an estimated 50 grams of formaldehyde. It is converted to formate by the enzyme formaldehyde dehydrogenase.2 Under ultraviolet radiation, formaldehyde is degraded in a few hours,3 and this is perhaps the main reason why formaldehyde does not accumulate in the environment. Interestingly enough, for astronomers, anyway, formaldehyde is found not only in earth’s biosphere, but in interstellar space and comet “tails.” Uses of Formaldehyde Formaldehyde has a number of applications in industry and in science, as well as in everyday life. Many resins and glues are synthesized using formaldehyde as a precursor and account for more than half of its 20 million metric tons yearly consumption. Three countries are responsible for half of the yearly global production: China produces one third of the total, the US produces 15% and Germany, 8%. Formaldehyde is also used to produce explosives. It is a raw material for the preparation of the military explosive RDX (Research Department eXplosive) that was widely used during World War II and is still common in many military applications. Scientific research takes advantage of the capability of formaldehyde to form crosslinks between primary amines (R-NH2) and nucleophilic groups such as other amines or carboxyl groups to fix tissues and store histology sections for long times. Formaldehyde’s crosslinking capability also allows one to covalently bind proteins to DNA thus affording the exploration by electron microscopy of the binding of proteins to DNA and the location of genes that are under the control of this or that regulatory protein. The capability of forming crosslinks allows scientist to “freeze” a macromolecule in a defined structure, and to study the effect of environmental conditions on the tertiary and quaternary structure of proteins and other macromolecules. The capability of formaldehyde to form crosslinks keeps isolated body organs from decomposing. This is generally performed by immersing the anatomical element in a 10% aqueous solution of formaldehyde that is called formol or formalin. In an extension of this type of usage, formaldehyde is also used in embalming and taxidermist fluids. The chemical capability to form crosslinks between biological molecules confers to formaldehyde the property of being a unique biocide able to kill bacteria and fungi, including sporulating ones. Formaldehyde and Safety Formaldehyde is volatile and flammable. It has a flash point of 185°F (85°C) and can explode with just the spark from an electric switch. It is therefore slightly dangerous when used without precaution, and its handling in industrial plants can be problematic. Chronic exposure to formaldehyde in air provokes irritation to the eyes and nose, headaches, and burning sensations in the throat, as well as difficulties in breathing. A study showed strong correlation between exposure to formaldehyde and childhood asthma development. Formaldehyde happens also to be an allergen and to cause dermatitis. Health agencies, such as the US Centers for Disease Control, consider formaldehyde to be a systemic toxin able to provoke permanent changes in the function of the nervous system. According to the Occupational Safety & Health Administration (OSHA), “…formaldehyde is a sensitizing agent that can cause a negative immune system response on exposure. It is highly irritating to the eyes, nose, and throat and can make anyone exposed cough and wheeze. Ingestion of formaldehyde can be fatal, and long-term exposure to low levels in the air or on the skin can cause asthma-like respiratory problems and skin irritation such as dermatitis and itching. Concentrations of 100ppm are immediately dangerous to life and health (IDLH). The National Institute for Occupational Safety and Health (NIOSH) considers 20 ppm of formaldehyde to be IDLH.” The Environmental Protection Agency recommends 0.1ppm of formaldehyde in air as the upper limit of safe indoor exposure. The International Agency for Research on Cancer (IARC-CIRC) classified formaldehyde as a known human carcinogen, associated with nasal sinus cancer and nasopharyngeal cancer. Personal Care Products And Formaldehyde Since formaldehyde is a gas, it cannot be added to finished products for personal care. Chemicals able to release formaldehyde once appeared to be the molecules of choice to use as preservatives in personal care because they can slowly release formaldehyde and maintain a preservative action over long times. Many cosmetic brands decided not to use them in their products because of safety issues. Other brands still use them. Common formaldehyde releasers likely to be found in a product include: DMDM hydantoin, methylene glycol, quaternium 15, and 3 dioxane, to name a few. These can be found in skin care products, and in hair care products, particularly salon products. Hair salon products might also contain chemicals that release formaldehyde when the product is heated, such as during flat-ironing or blow-drying. Other examples of chemicals that release formaldehyde include timonacic acid, dimethoxymethane, or decamethyl-cyclopentasiloxane. There are formaldehyde-free formulations available. When in a hair salon, ask to see an ingredient list. Some nail products can have high concentrations of formaldehyde in their formulations and release vapors that we can potentially inhale. According to Professor Corey L. Hartman, University of Alabama School of Medicine, the FDA doesn’t regulate the use of formaldehyde in skin care. “It recommends that it not be included at all in aerosols, and that other products contain no more than .2%. But those are merely recommendations and companies aren’t obligated to comply.” If formaldehyde is a concern and the formulator wants to avoid formaldehyde releasers, she must do her homework to identify brands that have clear lists of banned ingredients. Regulatory guidelines have been promulgated for the labelling of products containing or able to release formaldehyde. If a product contains 0.1% or more formaldehyde or releases at least 0.1ppm to 0.5ppm of it into the air, then the label must include: • Notice that the product contains formaldehyde. • Name and address of the manufacturer, importer and/or other responsible party. • Notice that physical and health hazards of the product are readily available from the employer and in the Safety Data Sheets. • If the product can release more than 0.5ppm of formaldehyde into the air, then the label must also include: • A list of all product health and safety hazards. The words “Potential Cancer Hazard” may be used prior to June 1, 2015. After June 1, 2015 the words “May cause cancer” must be used. Formaldehyde Paranoia? The dose makes the poison. This aphorism by Paracelsus should always be kept in mind when discussing the risks and the dangers associated with the use of a chemical. A publication by Lefebvre et al,4 sponsored by L’Oréal, the Dutch Organization for Applied Research (TNO), the European Cosmetic and Perfumery Association (COLIPA) and Beiersdorf describes the result obtained when measuring the air concentration of formaldehyde in a bathroom where several volunteers applied formaldehyde-releasing facial moisturizers, foundations, body lotions, deodorants, shampoo, hair conditioners and hair styling gels. In every case, and despite exaggerated exposure conditions, the measured concentration in air was about 5 micrograms per cubic meter. In normal conditions of temperature and pressure, one cubic meter of air has a mass of 1 kg so that the measured concentration of formaldehyde was about 0.005ppm, well below the 0.1ppm limit set by the EPA for safe indoor exposure. References
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