When it's smoggy outside, the ozone (O₃) responsible for the murk slips indoors, too, wafting through doors or ventilation systems. Once inside, the volatile oxygen molecule reacts with carpets, chemical cleaner residue and human skin.
In fact, according to new research published last week in Proceedings of the National Academy of Sciences, ozone coming into contact with human skin and hair, specifically the oils on each of them, sets off a whole lot of chemistry, some of it possibly of concern.
'Ozone and humans have been interacting since the dawn of man,' says chemist Charles Weschler of the Environmental and Occupational Health Institute in New Jersey, lead author of the study. But 'we found that when ozone reacts with skin oils you get a series of products, some of which have not been previously identified.'
One of those products, known as 4-oxopentanal, or 4-OPA, is structurally similar to diacetyl, perhaps better known as the popcorn-butter flavoring chemical that has caused serious lung issues for factory workers, known as 'microwave popcorn lung'. 'We don't know how toxic some of these compounds are,' Weschler says. '4-OPA's structure is similar to other dicarbonyls that we do know have adverse effects.'
It all started in airplanes
Weschler and colleague Armin Wisthaler of the University of Innsbruck in Austria first studied the issue of ozone in aircraft cabins. Whereas many larger planes have special filters to eliminate ozone, smaller planes, such as Boeing 737s, typically do not. The researchers hoped to determine what kinds of compounds were being produced when ozone interacted with the people and parts inside a jet.
On examination, the ozone proved to be largely interacting with one of the primary components of skin oils, the natural organic compound known as squalene, which is used as an adjuvant and moisturizer. Inside the body, squalene is the precursor of cholesterol, but the sebaceous glands in the skin churn out the stuff as is and ozone is drawn to it like a magnet, Weschler says.
In fact, it appears that squalene is the primary antioxidant protecting the skin from ozone, not vitamin E or other chemicals. 'I'm not a dermatologist,' Weschler says. But 'it's a very good thing we have squalene and these unsaturated fatty acids in our skin. I think it keeps other bad things from happening.'
In the new study, Weschler and Wisthaler first used proton transfer reaction mass spectrometry—a tool for detecting volatile organic compounds in air at levels of as little as a few parts per trillion—to determine what appeared after the squalene and ozone interacted. The interaction immediately produced acetone, geranyl acetone, hydroxy acetone and a compound known as 6-MHO—none of which are considered cause for health concern.
But some of those products go on to interact with yet more ozone in the air to form dicarbonyls—the aforementioned 4-OPA, plus 1,4-butanedial, 4-MON and 4-MOD. And it is these that might be cause for concern. 'We did not find these carbonyl products in the absence of ozone,' Weschler notes. 'It's not something we naturally emit.'
And all of them are possible lung irritants.
Testing pseudo–office workers
More than 35 million Americans complain of eye, nose or throat irritation when working indoors, costing the U.S. economy at least $20 billion annually in lost productivity. Some researchers have pinned the blame on indoor air pollution and a study last year showed that when outdoor ozone levels rose, the number of people inside suffering from so-called 'sick building syndrome' also increased.
So Weschler and Wisthaler simulated a typical office environment at the Technical University of Denmark in Copenhagen—two people in a carpeted 28.5–cubic meter room at a temperature of 23 degrees Celsius with two small stainless steel tables, two chairs, two flat-screen LCD monitors, two headsets, one walkie-talkie, one small mixing fan, a few books, two laptops, two bottles of water and ozone concentrations that reached roughly 32 parts per billion, an average exposure for a hot, smoggy day.
The squalene on these pseudo–office workers' skin soon began to interact with the ozone in the chamber. In fact, just one person in a similar size room removes as much as 25 percent of the ozone in the air, according to the results of the tests, turning it into various by-products. And, in cases where ozone preceded the people into the room, 4-OPA reached levels as high as two parts per billion after just four hours.

The question is: is that cause for concern?
No one knows, but the National Institute for Occupational Safety and Health (NIOSH) has begun testing. 'Do dicarbonyls in general have similar effects as diacetyl?' asks NIOSH chemist Ray Wells of the compound responsible for popcorn lung's chemical cousins. 'They are being formed but the concentrations that people are being exposed to we don't really know yet.'
NIOSH immunotoxicologist Stacey Anderson has begun testing dicarbonyls, 4-OPA in particular, to see if they provoke an immune reaction in mice or human lung cells. 'We have some promising results from that work in 4-OPA and others, some traditional markers for irritation,' such as cytokine levels, she says.
Weschler adds: 'The jury's still out on some of these oxidation products. Four-OPA might be of concern, some products that remain on skin might be irritating.' And it may be that the products have some kind of additive effect.
'It underscores the necessity to control ozone entry into buildings in regions with even moderate ambient ozone levels,' says environmental health scientist Michael Apte of Lawrence Berkeley National Laboratory in California. 'Likely, the findings in this paper contribute to an explanation of symptoms in the upper respiratory system and mucosa, and the lower respiratory system. It may explain skin-irritation symptoms.'
If that's the case, and a lot more research needs to be done to determine that, then there's a simple solution to sick building syndrome: 'You can shut this chemistry down by simply getting rid of the ozone,' Weschler notes, which can be accomplished with a simple charcoal filter in HVAC (heating, ventilating and air-conditioning) systems—a remedy currently being considered as a guideline by the American Society of Heating, Refrigerating and Air-Conditioning Engineers. 'If they wanted, they could take ozone out—and I'd like to see that happen.'

Today, the U.S. Food and Drug Administration is issuing a Safety Communication to inform patients and health care providers that devices claiming to clean, disinfect or sanitize continuous positive airway pressure (CPAP) devices or accessories (such as masks, tubing, headgear) using ozone gas or ultraviolet (UV) light are not legally marketed for this use by the FDA in the U.S., and as such, their safety and effectiveness for use with CPAP devices and accessories is unknown. CPAP devices are often prescribed for home use to patients with obstructive sleep apnea, a condition where an individual’s airway becomes blocked during sleep causing breathing to intermittently stop and start. CPAP devices use air pressure to keep airways open during sleep.

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To ensure the safe and effective cleaning of CPAP devices and accessories, the FDA is recommending that consumers and health care providers follow the cleaning instructions provided by the CPAP’s manufacturer, which normally include regular cleaning with soap and water.

“The FDA has identified several manufacturers that are marketing ozone gas or UV light-based products claiming to clean, disinfect or sanitize CPAP devices and accessories in the home,” said William H. Maisel, M.D., M.P.H, director of the Office of Product Evaluation and Quality in the FDA’s Center for Devices and Radiological Health. “Exposure to high levels of ozone gas may worsen a patients’ existing chronic respiratory diseases or increase the chance of a respiratory infection. UV light-based products could cause burns, eye damage or increase the risk of skin cancer due to over exposure. The FDA has contacted manufacturers of products making these claims and asked them to submit data demonstrating their safety and effectiveness.”

The FDA has received 11 reports from 2017-2019 from patients experiencing cough, difficult breathing, nasal irritation, headaches, asthma attacks and other breathing complaints when ozone gas-based products were used to clean, sanitize or disinfect CPAP devices and accessories. The FDA has not received any adverse event reports for UV light products claiming to clean, disinfect or sanitize CPAP devices and accessories.

Ozone is a gas that can be used to kill harmful bacteria. However, for ozone to be effective in killing harmful bacteria, it must be present at a concentration far greater than what is considered safe for humans. Although products claiming to clean, disinfect or sanitize CPAP devices that use ozone gas claim that they are designed to keep ozone gas inside the machine and its accessories, leaks can occur at tubing connections, filters or through containers used to house CPAP accessories. When leaks occur, ozone gas in the room where the devices are used may temporarily rise to unsafe levels especially if the room is small or not well ventilated.

Additionally, if the CPAP machine or accessories are used without first allowing fresh air to circulate through the entire CPAP system to remove any remaining ozone gas, this could lead to someone inhaling ozone gas, which could cause breathing problems.

Direct exposure to UV light may cause injury depending on its wavelength, intensity and exposure time. Additionally, the UV light may not be able to penetrate all components of CPAP devices and accessories, like the plastic tubing, masks and connectors, which could lead to inadequately disinfected components that may be unsafe for people to reuse.

While these devices claiming to clean, sanitize or disinfect CPAP machines and accessories have not been FDA cleared or approved for marketing in the U.S., the FDA conducted its own preliminary lab testing on several of those illegally marketed products. The testing demonstrated ozone-using disinfection devices generated ambient levels of ozone above limits considered safe for human exposure. Ozone levels were also high in CPAP machines and tubing even after waiting the amount of time recommended by the ozone-based device manufacturer after a cleaning cycle. The FDA’s studies also showed the power of the UV light and time during which CPAP masks and accessories were exposed to this light varied considerably among UV cleaners. If CPAP components are exposed to insufficiently strong UV light or processed for an insufficient amount of time, the CPAP components could be inadequately disinfected leading to safety and performance issues.

The FDA has contacted manufacturers of the ozone gas and UV light products that claim to clean, sanitize or disinfect CPAP devices and accessories. Each manufacturer was informed that based on their product’s intended use and technological characteristics, FDA review and clearance or approval is needed and that data would need to be provided to demonstrate safety and effectiveness.

The FDA will continue to monitor reports of adverse events associated with the use of ozone gas or UV-based CPAP devices that claim to clean, sanitize or disinfect CPAP devices and accessories and update the public should new information become available.

The FDA encourages individuals to report adverse events related to the use these devices to the FDA.

The FDA, an agency within the U.S. Department of Health and Human Services, protects the public health by assuring the safety, effectiveness, and security of human and veterinary drugs, vaccines and other biological products for human use, and medical devices. The agency also is responsible for the safety and security of our nation’s food supply, cosmetics, dietary supplements, products that give off electronic radiation, and for regulating tobacco products.

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