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Managing Asphyxiation Hazards from Cryogenic Gases
Issues to Consider for Safety, Monitoring, and Ventilation
BY SCOTT MYERS
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The hazards of asphyxiant gases are familiar to many safety and industrial hygiene professionals. These gases are present in certain industrial processes, and they must be considered before workers enter a confined space. This article presents best practices and common mistakes in managing the asphyxiant hazards associated with cryogenic fluids, which have the potential to rapidly displace oxygen due to their unique physical properties.
BACKGROUND Cryogens are compounds that exist as liquids at extremely cold temperatures and gases at standard temperatures and pressures. There is no universal agreement on how low the boiling point of a substance must be for it to meet the definition of a cryogenic fluid. According to the International Institute of Refrigeration, cryogens are fluids with boiling points below 120 Kelvin, or minus 244 degrees Fahrenheit, while the National Fire Protection Association (NFPA) defines the boiling point as below 183 K, or minus 130 F.
Cryogenic fluids are used in many industries, including aerospace, healthcare, food and beverage, biopharma, and technology. Hydrogen, methane, and oxygen are vital to spacecraft propulsion and life-support systems. Argon and nitrogen are used to control fire hazards and prevent oxidation in welding and other industrial processes. Liquid nitrogen is the most widely used cryogen, carbonating beverages, increasing the shelf life of perishables, and providing cryo-refrigeration for the long-term preservation of tissue cultures and other biological samples. Nitrogen has a boiling point low enough that it is used to supply ultra-low-temperature freezers for preservation of vaccines and biological samples, and it is more affordable and sustainable than helium.
Cryogenic fluids are commonly stored in small to medium-sized vacuum-insulated flasks—often referred to as “dewars” after their inventor, James Dewar—that minimize heat transfer and prevent condensation. Where substantial quantities of cryogenic fluids are needed, they are stored in large above-ground tanks, which are also designed with vacuum-insulated jackets. Insulation is vital for maintaining the cold temperatures at which the cryogens exist. Just as important to the cryogen supply system are foundation and support materials that can withstand the low-temperature effects of cryogen spills, pressure-relief systems to avoid over-pressurization of containers, emergency shutoff valves, and oxygen monitoring.
HAZARDS
Cryogens have multiple hazards that OEHS professionals need to be aware of. The expansion of cryogenic gases that boil off from cryogenic fluids results not only in oxygen deficiency but increased pressure that can rupture closed containers, launching debris at workers. An explosion of this nature can occur when, for example, cryogenic fluid leaks into the vials where biological samples are stored inside cryo-freezers, causing the vials to rupture when removed.
The extremely cold temperatures maintained by cryogens can rapidly freeze exposed skin, creating frostbite-like burns. Recommended personal protective equipment for dispensing and transferring cryogenic liquids include face shields and insulated gloves and aprons designed to protect skin from cold burns and flying debris. If additional protection is needed for the lower legs and feet—for example, when the potential for spills exists—insulated gaiters are available.
Due to nitrogen’s high liquid-to-gas expansion ratio, large supplies of dry nitrogen gas may be stored as liquids in smaller volumes. This common property of cryogens, which have expansion ratios ranging from 1:650 to 1:875, is responsible for one of the most insidious cryogen hazards: asphyxiation. Cryogens are simple asphyxiants, physically displacing atmospheric oxygen. They also have poor warning properties, boiling off colorless, tasteless, and odorless gases. In a 20-foot by 20-foot room with 9-foot ceilings, less than 150 liters of liquid nitrogen would displace the entire volume of air based on its expansion ratio of approximately 1:700. And it would take only 10 liters of liquid nitrogen—the contents of a small dewar—to displace sufficient air to lower the room oxygen below 19.5 percent, the OSHA definition of an oxygen-deficient atmosphere.
MONITORING Under normal operating conditions, gas boils off from the cryogenic fluid and escapes via pressure relief valves and other routes, such as when the fluid is transferred into containers or when samples are retrieved from cryo-freezer storage. The gas spreads on the ground in a cloud that is initially visible due to the presence of ice particles, which form as it freezes water vapor in the ambient air. Due to its density, the cloud displaces oxygen. A direct-read oxygen meter with a lower operating temperature of minus 4 F can detect oxygen deficiency within the cloud as it moves around the dewar or other containers and equipment.
For purposes of monitoring, it is important to consider the movement of this gas cloud and avoid placing oxygen monitoring sensors in areas that are not in a worker’s breathing zone. For example, a sensor located one foot above the floor or too close to the dewar or other cryogen-containing equipment will result in frequent alarms detecting oxygen deficiency that is highly localized. Workers become desensitized to constant alarms and eventually ignore them. The oxygen sensor should be located at the lowest breathing zone height in the room (for example, the height when a worker is seated) as determined by a risk assessment.
Oxygen monitoring systems should be installed and maintained to reliably detect and sound an alarm in the event of oxygen deficiencies in worker breathing zones. Oxygen sensors have limited service life and must be regularly calibrated, usually every one to three months, and replaced before the end of life on a preventive maintenance schedule, not upon failure. The most effective systems will not only alert workers in the immediate area but also notify security and facilities personnel through integration with the building management system.
It is not unusual to find indoor storage areas for cryogenic fluids that lack proper ventilation.
Even the best monitoring systems offer no increased safety if workers aren’t trained on the proper response to oxygen deficiency alarms. Workers must understand that the alarm indicates an emergency condition, requiring them to immediately exit or remain outside the monitored area. Employees should enter an area under an alarm condition only if they are on the emergency response team, equipped with appropriate respiratory protection, are properly trained to enter, and are actively searching for persons needing assistance because they have been incapacitated and cannot self-rescue. For unknown or IDLH (immediately dangerous to life or health) environments, OSHA requires either a full-face, pressure-demand, self-contained breathing apparatus (SCBA); or a combination full-face, pressure-demand, supplied-air respirator with auxiliary-contained breathing supply.
Low-oxygen alarms may initially indicate oxygen levels that are deficient but within the margin of safety, which is between 16 and 19.5 percent at altitudes less than 3,001 feet above sea level, according to ANSI/ASSE Z88.2-2015, Practices for Respiratory Protection. But levels could continue to drop below IDLH, when acute health effects become probable. As indicated in the Z88 standard, at 16 percent oxygen, workers may experience loss of coordination, impaired attention and thinking, and increased pulmonary ventilation and cardiac output. At 13 percent oxygen, abnormal fatigue, impaired judgement, and emotional upset may occur. At 10 percent oxygen, collapse and unconsciousness become possible. It is important to note that these percentages are based on work sites at sea level; work sites at higher elevations should account for the reduced atmospheric pressure and, accordingly, reduced partial pressure of oxygen (PO2).
NIOSH and ACGIH have defined oxygen deficiency as less than 132 torr PO2. The PO2 at the 5,300-foot elevation of Denver, Colorado, is close to 132 torr PO2, and the equivalent PO2 of 17.5 percent oxygen at sea level. While this low PO2 may seem alarming, workers living in Denver become well-acclimatized to these conditions within four weeks. As with heat illness prevention, due caution and monitoring is warranted for unacclimatized workers arriving at high-elevation work sites, especially when the lower available oxygen could be further reduced by off-gassing cryogens.
VENTILATION As with other atmospheric hazards, ventilation can be an effective engineering control for mitigating asphyxiation hazards when ventilation systems are properly designed. Ventilation design must account for the fact that gases boiling off from cryogenic liquids are extremely cold and denser than the ambient room air, causing them to sink to the floor. NFPA 55-2023, Compressed Gases and Cryogenic Fluids Code, provides specific ventilation guidance. It requires that indoor areas where cryogenic fluids are dispensed must be ventilated in accordance with the guidance in section 6.17 and mechanical code. Section 6.17 requires mechanical exhaust ventilation or fixed natural ventilation of at least 1 cubic foot per minute per square foot of floor space in indoor areas where cryogenic fluids are stored and used. Additionally, mechanical exhaust ventilation systems must account for the density of the gas: the exhaust air openings must be placed within 12 inches of the floor where gases heavier than air may be released. It’s crucial that exhaust air is not recirculated, as typical ventilation systems only filter particulates and would return asphyxiant gases to the occupied space.
Despite these standards, it is not unusual to find indoor storage areas for cryogenic fluids that lack proper ventilation. Without adequate management of change or hazard analysis, problems can arise when spaces intended for general occupancy are converted to areas for the storage or use of cryogens. The typical dilution ventilation systems found in general office occupancies have supply and return air openings in the ceilings and recirculate most of the air, doing little to remove the asphyxiant gases.
Modeling scenarios of incidental off-gassing, spills, leaks, and catastrophic failures can help the facilities design team understand the range of typical and worst-case oxygen displacement. This modeling may find that large-release scenarios could impact areas outside of the designated cryogen storage and usage zones, where ventilation systems may entrain and recirculate the gases. The audio and visual alarms associated with the oxygen monitoring systems may need to be extended to these areas to ensure that potentially impacted employees are alerted to oxygen-deficient conditions.
Proper ventilation is required to manage the asphyxiant hazard and shouldn’t be overlooked. Any administrative controls or PPE alone are likely to be infeasible, impractical, and inadequate to manage the risk when ventilation is lacking. Nonetheless, administrative controls, PPE, and preventive maintenance play important roles in ensuring the safe use of cryogenic fluids, particularly when ventilation failure, spills, or leaks occur.
INCIDENTS Risk assessments, hazard and operability (hazop) studies, or other effective risk evaluation processes are vital in identifying workplace hazards and operational problems that could arise from design and engineering issues in cryogenic systems. Taking a process safety management approach to break down complex process systems into simpler sections is especially helpful for larger cryogenic fluid distribution systems, which are plumbed throughout a facility to process equipment, dispensing stations, phase separators, pressure relief vales, and evaporators. To highlight the importance of careful risk analysis and management, it is helpful to discuss near misses, equipment failures, and accidents that have occurred at work sites, such as the following:
• A dewar containing liquid nitrogen exploded at Texas A&M University in 2006. Someone unaware of the hazards associated with unvented cryogenic fluid containers sealed a malfunctioning pressure-relief device. Approximately 12 hours later, the bottom of the dewar ruptured, and the force of the escaping pressure propelled the tank through the ceiling and pushed the laboratory walls off their foundations. 
• A pipe carrying liquid nitrogen ruptured at a Georgia poultry processing plant in 2021, resulting in six fatalities and 11 injuries. Lack of preventive maintenance and process safety management systems contributed to the accident, which was determined by the U.S. Chemical Safety and Hazard Investigation Board (CSB) to have resulted from the failure of the immersion freezer’s liquid level control system to accurately measure and control the liquid nitrogen level inside the freezer.
Proper training, preventive maintenance, and process safety management could have prevented these accidents.
RISK MANAGEMENT The innate hazards of cryogenic fluids, as well as the complexity of associated storage and distribution systems, serve well to illustrate the importance of effective risk assessment and management strategies familiar to OEHS professionals. Many relevant resources are available from industry associations, NFPA, CSB, and the Compressed Gas Association (CGA). Foregoing process hazard analyses, job safety analyses, and management of change procedures that can ensure appropriate hazard controls and facility procedures for cryogens is unnecessarily risky and can fail organizations and their workers.
SCOTT MYERS, CIH, CSP, CAC, is senior consultant, industrial hygiene and safety, for Citadel EHS in Seattle, Washington.
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RESOURCES
ACGIH: 2023 TLVs and BEIs Based on the Documentation of the Threshold Limit Values for Chemical Substances and Physical Agents (January 2023).
American National Standards Institute: ANSI/ASSE Z88.2, Practices for Respiratory Protection (2015).
Chemical Safety and Hazard Investigation Board: “CSB Releases Final Report into 2021 Fatal Liquid Nitrogen Release at Foundation Food Group Facility in Georgia” (December 2023).
National Fire Protection Association: NFPA 55, Compressed Gases and Cryogenic Fluids Code (2023).
OSHA: Occupational Safety and Health Standards, Personal Protective Equipment, Respiratory Protection.
Texas Department of Insurance: State Fire Marshal’s Alert, “University Campus Liquid Nitrogen Cylinder Explosion” (PDF, February 2006).