Carbon dioxide (CO2) makes up a relatively small percentage of atmospheric gases, yet when used or produced in large quantities as a gas, a liquid, or a solid (dry ice), substantial airborne exposures may occur. Exposure to elevated CO2 concentrations may elicit toxicity, even with oxygen concentrations that are not considered dangerous per se. Full-shift sampling approaches to measure 8-hr time weighted average (TWA) CO2 exposures are used in many facilities where CO2 gas may be present. The need to assess rapidly fluctuating CO2 levels that may approach immediately dangerous to life or health (IDLH) conditions should also be a concern, and several methods for doing so using fast responding measurement tools are discussed in this paper. Colorimetric detector tubes, a non-dispersive infrared (NDIR) detector, and a portable Fourier transform infrared (FTIR) spectroscopy instrument were evaluated in a laboratory environment using a flow-through standard generation system and were found to provide suitable accuracy and precision for assessing rapid fluctuations in CO2 concentration, with a possible effect related to humidity noted only for the detector tubes. These tools were used in the field to select locations and times for grab sampling and personal full-shift sampling, which provided laboratory analysis data to confirm IDLH conditions and 8-hr TWA exposure information. Fluctuating CO2 exposures are exemplified through field work results from several workplaces. In a brewery, brief CO2 exposures above the IDLH value occurred when large volumes of CO2-containing liquid were released for disposal, but 8-hr TWA exposures were not found to exceed the permissible level. In a frozen food production facility nearly constant exposure to CO2 concentrations above the permissible 8-hr TWA value were seen, as well as brief exposures above the IDLH concentration which were associated with specific tasks where liquid CO2 was used. In a poultry processing facility the use of dry ice to quickly freeze product produced a nearly constant CO2 concentration that caused exposures to approach the permissible 8-hr TWA exposure value.