Journal of Occupational and Environmental Hygiene

ISSN: 1545-9624 (Print) 1545-9632 (Online) Journal homepage: http://oeh.tandfonline.com/loi/uoeh20

Exposure Assessment for Carbon Dioxide Gas:

Full Shift Average and Short-Term Measurement
Approaches

R. Jedd Hill & Philip A. Smith

To cite this article: R. Jedd Hill & Philip A. Smith (2015) Exposure Assessment for
Carbon Dioxide Gas: Full Shift Average and Short-Term Measurement Approaches,
Journal of Occupational and Environmental Hygiene, 12:12, 819-828, DOI:
10.1080/15459624.2015.1053894

To link to this article: http://dx.doi.org/10.1080/15459624.2015.1053894

Accepted author version posted online: 29

May 2015.
Published online: 03 Nov 2015.

Submit your article to this journal

Article views: 43

View Crossmark data

Full Terms & Conditions of access and use can be found at

http://oeh.tandfonline.com/action/journalInformation?journalCode=uoeh20

Download by: [152.180.134.66] Date: 04 November 2015, At: 07:45

 Journal of Occupational and Environmental Hygiene, 12: 819–828
ISSN: 1545-9624 print / 1545-9632 online
DOI: 10.1080/15459624.2015.1053894

Exposure Assessment for Carbon Dioxide Gas: Full Shift

Average and Short-Term Measurement Approaches
R. Jedd Hill and Philip A. Smith
U.S. Department of Labor, OSHA, Health Response Team, Sandy, Utah

Carbon dioxide (CO2 ) makes up a relatively small percent-

age of atmospheric gases, yet when used or produced in large Address correspondence to Jedd Hill, OSHA Health Response
quantities as a gas, a liquid, or a solid (dry ice), substantial Team, Salt Lake Technical Center, 8660 S. Sandy Parkway, Sandy,
airborne exposures may occur. Exposure to elevated CO2 con- UT, 84070; e-mail: hill.jedd@dol.gov
Downloaded by [152.180.134.66] at 07:45 04 November 2015

centrations 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 sev-
eral 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 fluctu-
ations 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 ex-
posures 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.
Keywords carbon dioxide, Fourier transform infrared analysis,
immediately dangerous to life or health (IDLH), nondis-
persive infrared detection, time-weighted average sam-
pling, grab sampling
Color versions of one or more of the figures in the article can be
found online at www.tandfonline.com/uoeh.
INTRODUCTION
Properties and Hazards of Carbon Dioxide (CO2 )
At typical atmospheric temperature and pressure carbon
dioxide (CO2 ) is a gas, but it may be liquefied with increased
pressure. Its specific gravity is 1.52 relative to air,(1) and CO2
gas readily migrates to low elevations when not well-mixed.
It is colorless, odorless, and non-flammable, and solid CO2
(dry ice) sublimes directly to gas. Relatively pure CO2 is
inexpensive; it is commonly transported in a compact liquid
volume, and dry ice may be created from the liquid at a point
of use.
Liquid CO2 and dry ice are widely used where rapid cooling
of materials is desired. For example, it is important to rapidly
freeze products during large scale preparation of frozen food
to eliminate conditions conducive to microbial growth (see
Figure 1). Also, sublimation of dry ice directly to gas allows
for rapid cooling of product packed in boxes, without the
potential for water damage to product or packaging.
Ikeda et al. demonstrated that CO2 is not a simple asphyxi-
ant, as a mixture where CO2 replaced nitrogen in air (with 20%
oxygen) was fatal to dogs within 1 minute.(2) Effects related
to CO2 exposure can range from relatively minor problems to
respiratory distress and death. Breathing rate is affected and
often increases as airborne CO2 concentrations increase, and
headache, dizziness, and increased blood pressure and heart
rate may also occur.(3) A generalized weakness and feeling of
lethargy(4) is noted with CO2 intoxication, and a depressive

Journal of Occupational and Environmental Hygiene December 2015 819


Downloaded by [152.180.134.66] at 07:45 04 November 2015
FIGURE 1. Application of liquid CO2 directly to recently-cooked
food to rapidly lower the product temperature. Liquid CO2 was
passed through the conical-shaped applicator (top, foreground),
and an ineffective local exhaust hood is visible immediately to the
rear of the applicator. Even though CO2 is a clear gas, during
chilling with liquid CO2 a visible fog thought to be related to chilled
water vapor may be seen in nearby areas with high CO2 air
concentrations.
effect to both the circulatory and respiratory systems has been
described with exposure to high CO2 concentrations.(2) It has
been reported that “exposure at 7–10% produces unconscious-
ness within a few minutes.”(1)
Dangers associated with CO2 are found in many settings.
It is used for inerting, shielding, as a fire suppressant, and for
carbonation of beverages. In addition to being a product of
fermentation, CO2 may be added to beer during brewing to
purge oxygen for control of fermentation. It may be used in
greenhouses for optimization of plant growth, and has been
used as a pest control fumigant. Organic chemicals are soluble
in supercritical CO2 which has been used to selectively extract
caffeine from coffee beans avoiding use of liquid solvents.
High CO2 levels may be encountered in below-ground sewer
system manholes and utility vaults. Smith et al. recently re-
ported on a number of distinct fatality cases related to CO2 in
new-construction manholes not connected to an active sewer
or drain system.(5)
Occupational Exposure Limits for Airborne CO2
The U.S. Occupational Safety and Health Administration
(OSHA) permissible exposure limit (PEL) as an 8-hr time-
weighted average (TWA) exposure for CO2 is 5,000 ppmv
(0.5%),(6) and the American Conference of Governmental In-
dustrial Hygienists (ACGIH) has published a 5,000 ppmv TWA
threshold limit value (TLV) and a 30,000 ppmv (3%) short-
R
term exposure limit (STEL).(7) While OSHA has not promul-
820 Journal of Occupational and Environmental Hygiene
gated STEL, ceiling, or peak CO2 standards, exposures at or
above 40,000 ppmv (4%) are considered by the U.S. National
Institute for Occupational Safety and Health (NIOSH) and
OSHA to be immediately dangerous to life or health (IDLH).(8)
While the only explicit OSHA exposure standard for CO2
pertains to 8-hr TWA measurements, the potential for IDLH
conditions must be considered when CO2 is used or generated
in large quantities, or when it is introduced into poorly ven-
tilated spaces. The OSHA respiratory protection standard(9)
generally requires the use of a self-contained breathing ap-
paratus (SCBA) or supplied air respirator with self-contained
escape capability for IDLH exposures. As it is a permanent gas
at equilibrium in the workplace, airborne CO2 concentrations
up to 100% are possible.
As with other stressors where both full shift and short-
duration exposure information is of interest, a TWA sample av-
eraged across an 8-hr workday may indicate acceptable expo-
sure below the OSHA PEL value for CO2 , even with multiple
short-duration excursions above 4% CO2 . Thus, two exposure
assessment problems exist for CO2 : the identification and
measurement of 8-hr TWA exposures, and the identification
and measurement of sudden short-duration CO2 concentration
increases when IDLH conditions are possible. Measurement
of both exposure types may be needed for selection of proper
engineering controls and interim protective equipment.
Airborne CO2 Measurement
Full-Shift TWA CO2 Measurement
Modern sampling methods for airborne CO2 are atypi-
cal, as a sorbent is not used to concentrate the target ana-
lyte from sampled air. Instead, the OSHA personal sampling
method(10) involves collection of a TWA air sample in a five-
layer aluminized bag, with the bag shipped for laboratory gas
chromatography (GC) analysis. A NIOSH method(11) is very
similar, although field-portable GC analysis is emphasized.
Documentation for the OSHA method indicates that only five-
layer aluminized bags should be used, and no more than a 10%
sample loss is expected if bags are analyzed within 14 days of
sampling.(10) Figure 2 shows a worker wearing a bag which is
attached to a sampling pump which must include an additional
outlet hose connection (hose barb) in addition to the normal
breathing zone hose inlet connection. The pump outlet hose is
routed to a five-layer aluminized bag which may be taped to a
worker’s back.
CO2 Measurement in the Field
Colorimetric detector tubes provide a simple and inexpen-
sive method to quickly determine airborne CO2 concentrations
with a simple color change reaction. A fixed air volume is
drawn through a tube using a compact and highly portable hand
pump without the need for electrical power. Technician-level
operators may be trained in detector tube use and interpreta-
tion of results, a tube/hand pump combination is intrinsically
safe, and detection ranges from below typical ambient CO2
concentrations to high percent values are available.
December 2015

Downloaded by [152.180.134.66] at 07:45 04 November 2015
FIGURE 2. Personal TWA sampling for CO2 exposure using a
low-flow pump with outlet hose barb (pump not visible) and a five-
layer aluminized bag.
Another method for nearly instantaneous determination of
airborne CO2 concentration involves the molecular absorbance
of infrared (IR) energy. Absorbance at a correctly chosen IR
wavelength is mathematically related to the gas phase CO2
concentration when Beer-Lambert law conditions are met. A
CO2 -specific detector that employs only a narrow wavelength
band relevant to this gas (e.g., the asymmetrical stretch band
for CO2 occurring near 4.3 µm) is termed a non-dispersive
IR (NDIR) detector, and several manufacturers offer handheld
NDIR instruments for airborne CO2 measurement.
Absorbance-based detection is also possible with a more
complicated gas-phase Fourier transform infrared (FTIR)
spectroscopy instrument that uses an interferometer to rapidly
scan a wide range of wavelengths. Quantitation of airborne
CO2 concentrations is possible with gas-phase FTIR
spectroscopy, and the simultaneous quantitation of a limited
number of other analytes is also possible with a modern field-
portable FTIR instrument. The operating principles of field-
portable gas-phase FTIR spectroscopy instrumentation were
recently described by Heikkilä.(12)
Objective
This article provides performance information for several
quantitative field detection methods based on laboratory work
completed using dynamically generated CO2 standards in dry
and humid air. Approaches used to measure both full shift
Journal of Occupational and Environmental Hygiene
TWA and nearly instantaneous short-term CO2 exposure con-
centrations are discussed, and data resulting from the use of
both approaches are presented from three workplaces where
CO2 was either produced or used in large amounts.
MATERIALS AND METHODS
Collection of Whole-Air Samples
Whole-air samples were collected in 5-layer aluminized
bags (10 L volume, Cali-5-BondTM, Calibrated Instruments
Inc. Hawthorne, NY). Suitable pumps were used for personal
8-hr TWA CO2 sampling (Twin Port Pocket Pump, Model
210-1002A, SKC Inc. Eighty Four, PA). Inlet tubing was
secured within a worker’s breathing zone with care taken
to avoid capture of directly-exhaled CO2 (Figure 2). Pumps
were calibrated before and after use using a timed volume
displacement device (DC-lite, BIOS International, Butler, NJ),
with pre- and post-sampling flow verified to be within ± 5%.
Bags were also used with a vacuum box (Vac-U-Chamber,
SKC Inc.) to collect whole-air grab samples, except at the
brewery where air was directly sampled into a 2 L syringe
with immediate transfer into 5-layer aluminized bags. Vacuum
was applied to the sealed box with a bag inside which was
connected to the atmosphere through tubing that passed to the
exterior, allowing whole-air sample collection in < 30 sec.
Laboratory Analysis
Whole-air samples were shipped to the OSHA Salt Lake
Technical Center Industrial Hygiene Chemistry Division lab-
oratory, where a model 6890 GC instrument (Agilent Tech-
nologies, Wilmington, DE) with a pulsed discharge detector
(model D-3, Valco Instrument Company, Houston, TX) was
used to complete analyses. Bag contents were pumped into
a 1.0 mL offline sample loop, and helium carrier gas flow
(99.999%, Praxair, Salt Lake City, UT) was aligned to inject
sample loop contents. Injector temperature was 200◦ C, and a
50:1 split ratio was used. The porous layer open tubular column
(RT-QPLOT, Restek, Bellefonte, PA, 30 m × 0.32 mm i.d.)
was maintained at 35◦ C throughout an analysis event, with
carrier gas linear velocity of 50 cm/s.
Colorimetric CO2 Detector Tubes
Quantitation ranges for the CO2 detector tubes used were
0.13–6% (2L,Gastec Corporation, Kanagawa, Japan) and
0.5–20% (2H, Gastec Corporation). Tubes were used to select
locations and individuals for grab sampling, but as a detector
tube requires preparation followed by operation of a hand
pump, this approach was used when the NDIR detector used
(see below) was not available to provide continuous CO2
concentration information.
Detector tubes were evaluated in the laboratory with low
(13.1 ± 1.8%) and high (80.1 ± 1.4%) humidity air at six
CO2 concentrations (0.48–11.4%). Air was drawn through a
single tube at each concentration/humidity combination us-
ing the recommended hand pump, and manufacturer read-
ing/correction instructions were followed. The 2L tubes have
December 2015 821
 been subjected to third party certification by Safety Equipment
Institute, Inc. (SEI) to meet standards of accuracy and repro-
ducibility,(13) closely following an earlier NIOSH detector tube
certification program.(14)
Handheld NDIR CO2 Detector
A handheld NDIR instrument (GD444/10, CEA Instru-
ments, Inc., Westwood, NJ) provided near real-time
measurements for airborne CO2 in the facilities visited for on-
site safety, to identify work processes where transient IDLH
conditions existed, and to identify workers for TWA sam-
pling. A small on-board pump drew air through a sample
cell, and absorbance near 4.3 µm provided CO2 concentration
estimates, with readings continuously updated. The manufac-
turer’s stated accuracy is 2% (full scale), with concentration-
dependent resolution: 50 ppmv (1,000–5,000 ppmv ), 100 ppmv
(5,000–7,000 ppmv ), 200 ppmv (7,000–10,000 ppmv ), and
0.1% (1.0–10% by volume).
After calibration under the prevalent atmospheric pressure
Downloaded by [152.180.134.66] at 07:45 04 November 2015
this instrument was evaluated in the laboratory with low (12.7
± 0.8%) and high (80.2 ± 0.4%) humidity air at 5 CO2 concen-
trations (0.48–7.38%). Ultra-high purity N2 (UHP, 99.999%,
Praxair) and 5.0% CO2 (99%, Praxair) in dry N2 were used for
calibration.
Field-Portable FTIR Spectroscopy
Following TWA and grab sampling in the field at the frozen
food and poultry processing facilities, aliquots of collected
air were subjected to on-site FTIR analysis with a gas-phase
FTIR instrument (DX-4015, Gasmet Technologies, Helsinki,
Finland). Reference spectra obtained with CO2 mixed in an
IR-opaque gas were needed for quantitation, and ten refer-
ence spectra ranging from 0.05–1.0% CO2 supplied by the
manufacturer were used for field work and initial work in the
laboratory.
Spectral resolution was 8 cm−1, with 10 scans · s−1 collected
from 900–4,200 cm−1. Sample cell temperature was 50◦ C, and
sample cell pressure was recorded by the instrument. The
flow rate of the internal pump was 2.9 L/min, and while
operated in the field it was set to run for 30 s to fill the
0.4 L sample cell, followed by scans over 60 s (600 scans)
which were averaged to determine CO2 concentration based
on absorbance from 2,000–2,250 cm−1. In the field, three
pumping/measuring cycles were completed and the final anal-
ysis result was recorded. Following creation of five additional
reference spectra (0.145–7.23% CO2 ) instrument performance
was evaluated in the laboratory with low (20.6 ± 1.3%) and
high (80.2 ± 0.7%) humidity air, at seven CO2 concentrations
(0.24–7.0%).
The potential for exhaled CO2 to bias full shift whole-air
sampling was examined using a flexible tubing inlet for the
FTIR instrument that could be moved to different breathing
zone locations. Measurements were completed for exhaled air
samples (with the inlet tube placed in an author’s mouth during
exhalation), breathing zone air samples 5 cm away from an
author’s mouth and to the side of the face, and breathing zone
822 Journal of Occupational and Environmental Hygiene
air samples 18 cm away from an author’s mouth and to the side
of the face resting on a shoulder (as with the sampling train
inlet placement used for full shift field sampling). The on-board
sampling pump operated continuously and scan averaging time
was 5 s for these measurements.
CO2 Standard Generation
A glass flow-through system was used to generate test
standards in the laboratory, with CO2 and air blended in a
mixing cell at 21◦ C. Mixed gas flowed upwards, turning 90◦
to enter a sampling plenum, where temperature and relative
humidity were measured using an MP75 relative humidity and
temperature probe (Vaisala Oyj, Helsinki Finland) connected
to an M170 measurement indicator (Vaisala Oyj). Volumetric
CO2 flow was measured using a timed volume displacement
device (DC-lite, BIOS International), while the much greater
dilution air flow was measured using a dry gas meter (DTM-
200A, Singer American Meter Division, Franklin Lakes, NJ)
by timing delivery of 10 L air. Water vapor content was
controlled with a flow, temperature, and humidity control
system (HCS-401, Miller-Nelson Research, Monterey CA).
By varying CO2 and humidity-controlled dilution air flows in
the mixing cell, CO2 concentrations generated ranged from
0.24–11.4%. To create reference spectra for the FTIR instru-
ment, UHP N2 replaced dilution air in this system.
RESULTS AND DISCUSSION
Laboratory Evaluation of Field Quantitation
Approaches
Detector Tubes
When used in both dry and humid air the detector tube
measurements fell within the applicable accuracy parameters
for exposures at or above the current ACGIH TLV value
as an exposure standard, as set forth in the joint American
National Standards Institute/International Safety Equipment
Association (ANSI/ISEA) standard for gas detector tube per-
formance.(15) This standard is used by SEI for detector tube
certification,(13) and is based upon parameters specified in
the earlier NIOSH program.(14) To fully meet accuracy re-
quirements a detector tube must read ± 25% of the true air
concentration value at 1, 2, and 5 times the relevant ACGIH
TLV (which for CO2 is identical to the OSHA 8-hr TWA
PEL value), and ± 35% of the true air concentration value at
0.5 times that value. Tubes were not evaluated at 0.5 times
the TLV value, as our field work was focused on detection
of CO2 concentrations > the OSHA PEL value. While only
the low range Gastec tubes are SEI-certified, both the low and
high range CO2 tubes produced readings that deviated from
the concentration sampled by no more than 23%, and in most
cases the readings were more accurate (Table I).
Figure 3 shows that detector tube readings obtained in the
laboratory were highly correlated with CO2 concentration
sampled for all four tube/humidity combinations listed in
Table I. The precise color change front location within a tube
is somewhat subjective as single whole digit concentration
December 2015
 TABLE I. Comparison of Colorimetric Tube Percent CO2 Readings to the Concentrations Produced by the
Flow-Through Standard Generator System
%CO2 Concentration/ 2L Tube 2H Tube
Conditions Result (%) % difference Result (%) % difference
0.48/dry 0.46A −4.3 0.46B −4.3
0.48/humid 0.47A −2.1 0.59B 23
0.84/dry 0.75A −11 0.81B −3.6
0.84/humid 0.88A 4.8 0.93B 11
3.67/dry 3.3C −10 3.1A −16
3.62/humid 3.4C −6.1 3.4A −6.1
5.27/dry 4.5C −15 —D
5.20/humid 5.2C 0 4.9A −5.8
7.42/dry — E
5.9 A
−20
7.44/humid —E 7.0A −5.9
11.0/dry —E 9.3C −15
11.4/humid —E 10.1C −11
Downloaded by [152.180.134.66] at 07:45 04 November 2015

Note: Readings were corrected for atmospheric pressure at the laboratory site following directions provided by the tube manufacturer. The percent differences
between the corrected tube readings and the CO2 concentrations sampled are provided in the third and fifth columns. AMeasured using a single full pump stroke
(100 mL); BMeasured using two full pump strokes (2 × 100 mL); CMeasured using one-half pump stroke (50 mL); DMeasurement not taken;EBeyond measurement
range.

increments are marked on a 2H tube (as is also the case for most
2L tube markings). Values shown in Table I were obtained by
determining the color change front against the printed scale on
a tube to the nearest 1/10th marking interval, and this value was
then subjected to correction. For example, the reading of 3.3%
for the 2 L tube (dry air) from the measurement of 3.67% CO2
was read as 1.4%, but this was doubled to 2.8% as only one-
half pump stroke was used. This value was then corrected for
the laboratory atmospheric pressure of 653 mm Hg (2.8% was
multiplied by 760 mmHg/653 mm Hg) to obtain the corrected
reading of 3.3% CO2 . The detector tube manufacturer does
not list water vapor as an interference for either tube, and
no attempt was made to explore the apparent difference in
tube response between dry and humid airborne CO2 standards
sampled.
NDIR Detector
Figure 4 shows that NDIR readings were highly correlated
with the CO2 concentrations sampled. The NDIR detector
readings obtained in the laboratory deviated by no more than
7.8% from the CO2 concentrations sampled.

FIGURE 3. Results from laboratory analyses using the col-
orimetric detector tubes described in the text for varied CO2
concentrations created with the flow-through standard generator.
The dark circles and triangles, respectively, represent the 2L
and 2H detector tubes used with dry air standards, while the
white circles and triangles, respectively, represent the 2L and 2H
detector tubes used with humid air standards.
FTIR Spectroscopy
Figure 4 shows that the readings obtained through FTIR
spectroscopy were highly correlated with the concentration of
CO2 sampled. The FTIR instrument produced readings in the
laboratory that deviated from the CO2 concentration sampled
by no more than 9.2%.
Examination of exhaled air by FTIR analysis showed CO2
content of about 4%, while the background CO2 concentration
in the room where the measurements were made was 0.06%.
With the FTIR inlet tubing placed only 5 cm away and directly
to the side of each author’s mouth the CO2 concentrations
measured ranged between 0.10 and 0.11%. When the distance
between inlet and mouth was increased to 18 cm with the inlet
resting on a shoulder at a height just below the mouth (as was
the case for full shift sampling of workers completed in the
field) the CO2 concentrations measured were identical to the
room air background CO2 conentration.

Journal of Occupational and Environmental Hygiene December 2015 823

 TABLE II. Results for Personal 8-hr TWA Sampling
of Brewery Cellar Workers for CO2 Exposure
Sample TWA CO2
Duration (min)A Exposure SeverityB
435 0.84
442 0.48
405 0.75
405 0.38
442 0.49C
436 0.46
374 0.35
365 0.31
420 0.47

FIGURE 4. Results from laboratory analyses using the field-
portable FTIR instrument (circles) and the handheld NDIR detector
(triangles) for both dry (darkened symbols) and humid (white
symbols) CO2 standards created with the flow-through standard
Downloaded by [152.180.134.66] at 07:45 04 November 2015
Note: Work included general maintenance, and tank emptying and cleanup.
AA single bag was used for both morning and afternoon sampling with
pump and bag removed from employee and pump turned off with bag inlet
valve closed during lunch break. Unsampled time at end of shift included

generator. duties without potential for elevated CO2 exposure. B1.0 = 0.5% CO2 as 8-hr
TWA; unsampled time counted as zero CO2 exposure. CThis sample included
exposure known to exceed 4% CO2 .
Field CO2 Measurements and Laboratory Analysis
Results for Whole-Air Samples
Brewery
handheld NDIR detector, and the IDLH conditions were con-
Cellars of the brewing facility were located within several
firmed through laboratory analysis of whole-air grab samples
multi-story buildings, and workers performed tasks there, and
(Table III).
also spent substantial time in a lounge area of a separate
Riley and Bromberger-Barnea reported on similar work in
building while awaiting assignments. After newly brewed beer
1979, and noted with regard to draining a tank that “. . .CO2
in a large tank (>105 L) was removed for further processing
which is heavier than air, pours out of the door almost like
it was necessary to empty liquid and solids remaining at the
a liquid. The CO2 concentration may thus be much higher
tank bottom. An access hatch was opened at the lowest level
closer to the floor than at normal breathing height.”(16) This
of a tank, allowing light brown opaque liquid and solids to
matches our observations, as CO2 concentrations just above
flow onto the floor in front of a tank, and then to a floor drain.
liquid being drained typically exceeded the IDLH value, but
Tank ventilation commenced after draining to allow entry for
on some occasions IDLH conditions at worker breathing zone
cleaning.
height were also identified.
During an initial survey in the cellars, CO2 levels near
2% were detected in some areas using the handheld NDIR Frozen Food Production Facility
instrument, and CO2 concentrations throughout the cellars Several kitchen areas were located in rooms adjoining a
were measured to be near or above the 0.5% OSHA PEL value. large open bay area within the frozen food production facility.
Consistent with the results of previous full shift TWA personal Food products were prepared separately in a kitchen, with
sampling completed by safety personnel at the brewery, 8-hr
TWA CO2 exposures did not provide evidence for overexpo-
sure expressed as exposure severity (Table II, 100% of 8-hr
TABLE III. Results for Laboratory Analysis of
TWA PEL = 1.0), presumably due to CO2 concentrations
Whole-Air Grab Samples Collected during Two Brew-
in the lounge area being much lower than the PEL value
ery Tank Opening Procedures
for CO2 .
However, tank draining was shown in several instances to Laboratory
be associated with airborne CO2 concentrations greater than Sample Height Analysis Result (% CO2 )
the IDLH value, and workers assigned to open tanks without
respiratory protection knew from experience to quickly leave Chest Height 8.0
the area in front of an access hatch after opening. Although Floor LevelA 10.7
a worker tended to not linger directly in front of a tank ASample obtained with inlet to the large syringe used to collect whole-air
opening, he or she would stay close enough to spray water samples just above liquid present on the brewery floor after being drained
at the hatch opening and the nearby floor. Airborne CO2 con- from a tank. While this grab sample was collected the CO2 concentration at
centrations which exceeded 4% at breathing zone level were chest height and breathing zone was indicated to be < 4% by measurement
identified in several instances using both detector tubes and the using the handheld NDIR detector.

824 Journal of Occupational and Environmental Hygiene December 2015

 TABLE IV. Field Measurements Obtained for Air- bowl was sealed with a clear plastic cover and was pushed onto
borne CO2 Concentrations Using the Handheld NDIR a conveyor belt into a liquid CO2 chiller. After traveling on an
Detector Near Pneumatic Dispensing/Sealing Ma- internal conveyor system in a spiral path from bottom to top,
chinery in the Frozen Food Production Facility Open bowls containing frozen product travelled back to bench top
Bay Area level where workers packaged the bowls. The interior of the
spiral flash chiller emptied to the outdoors, although visible
Time of Measurement/ Field Measurement CO2 leaks into the open bay area were observed where gaskets
Pneumatic Machinery Status Result (% CO2 ) did not completely seal access hatches.
09:46 am/machinery not operating 0.88 Detector tubes and the handheld NDIR detector indicated
09:55 am/machinery operating 1.7 elevated CO2 readings in the open bay area before any pack-
10:40 am/machinery operating 1.8 aging or flash freezing commenced (Table IV). The pneumatic
01:22 pm/machinery not operating 0.62 machinery was found to be operated using CO2 gas, with
leaky connections causing the high CO2 background. Airborne
CO2 concentrations near the machinery exceeded the OSHA
8-hr TWA PEL value before and after dispensing/sealing of
ingredients such as rice and ground meat immediately mixed cooked product, while CO2 concentrations increased to several
there with liquid CO2 applied during mixing to quickly cool multiples of the PEL value during dispensing/sealing. Results
the product (see Figure 1). Individual items were formed by of 8-hr TWA sampling expressed as exposure severity (Ta-
ble V) confirmed that overexposure to the PEL value was
Downloaded by [152.180.134.66] at 07:45 04 November 2015

hand from the bulk material into ball shapes with 5–6 cm
diameter, which were placed onto trays that were wheeled into
a walk-in chiller adjacent to the kitchen. The chiller door was
closed and liquid CO2 was sprayed inside to flash freeze the
product. Local exhaust ventilation in the kitchens where liquid
CO2 was used during mixing was limited to flexible hose
lines, as seen behind the liquid CO2 applicator in Figure 1.
A duct to the exterior existed from the walk-in chiller, but
with no fan present to remove CO2 gas following use of the
chiller.
Other products were combined in the open bay area after
being cooked in a kitchen. Pneumatically operated machinery
dispensed liquid (e.g., stew liquid) onto solid items (e.g., meat,
vegetables, and rice) inside individual serving-sized bowls, and
moved the bowls through this process. Bowls containing solid
items were passed under a nozzle for addition of liquid, then a
nearly certain for packagers working a substantial portion of
a full shift near the pneumatic machinery. After accounting
for sampling and analytical error, an 8-hr TWA overexposure
to CO2 for which a citation could be issued was narrowly
avoided for a U.S. Department of Agriculture Food Safety
Inspection Service (FSIS) employee who only spent a portion
of the day in the open bay area. Airborne CO2 concentrations
in the separate kitchen areas were mostly below the 8-hr TWA
PEL value (except when liquid CO2 was in use—see below),
with workers preparing food in the kitchen areas generally
experiencing lower 8-hr TWA exposures.
Two separate circumstances were observed to produce
IDLH CO2 concentrations, with the first being the opening
of the walk-in chiller after use. When this occurred, airborne
CO2 was measured in the adjoining kitchen area at

TABLE V. Laboratory and Field FTIR Analysis Results for Personal 8-hr TWA Sampling of Cooks (Working in
Kitchens), Packagers (Working Near Pneumatic Machinery), and FSIS Inspector for CO2 Exposure
SampleA 8-hr TWA CO2 B Field FTIR Analysis Laboratory Analysis
Duration (min) Exposure Severity Result (% CO2 ) Result (% CO2 ) Primary Task
454 1.0 0.54 0.54 FSIS inspector
446 1.4C 0.74 0.73 Cook
440 0.7 0.44 0.36 Cook
402 0.9 0.56 0.53 Cook
484D 1.7 0.83 0.82 Packager
425 D 1.4 0.80 0.79 Packager
423 D 1.7 0.97 0.97 Packager
441 D 1.9 1.01 1.01 Packager
432 D 1.9 1.08 1.08 Packager
440 D 1.2 0.65 0.63 Packager
AA single bag was used for both morning and afternoon sampling with pump and bag removed from employee and pump turned off with bag inlet valve closed

during lunch break. B1.0 = 0.5% CO2 as 8-hr TWA; full shift sample, based on laboratory analysis results; unsampled time counted as zero CO2 exposure. CThis
sample included exposure known to exceed 4% CO2 . DUnsampled time at beginning or end of shift likely to include CO2 concentrations >0.5% due to elevated
CO2 concentrations in the open bay area near pneumatic machinery.

Journal of Occupational and Environmental Hygiene December 2015 825

 TABLE VI. Results for Grab Samples Related to
IDLH Exposures Detected at the Frozen Food Pro-
cessing Facility: Laboratory and Field FTIR Analyses
Field FTIR Laboratory
Sample Analysis Analysis
Location Results (% CO2 ) Results (% CO2 )
Kitchen areaA 10.1 9.79
Kitchen areaB 8.56 6.64
RestroomC 4.92 —D
AChest height in kitchen area following opening of walk-in chiller as described
in text. BNear floor drain in kitchen during application of liquid CO2 for
cooling freshly cooked product as described in the text. CSample collected at
breathing zone height of a sitting person, with CO2 entering the restroom
through the grated floor drain as described in text. DBag leaked during
shipping.
Downloaded by [152.180.134.66] at 07:45 04 November 2015
concentrations > 10% using the handheld NDIR detector, and
at 9.79% by laboratory analysis of a grab sample. Regarding
the second IDLH exposure situation, grated drain channels
existed throughout the building and CO2 gas flowed through
a drain channel to enter a restroom adjacent to a kitchen area
due to a small fan that continuously exhausted air from the
restroom. Using the handheld NDIR detector, CO2 concentra-
tions > 4% were detected near the floor of the kitchen and
within the drain channel while liquid CO2 was used, and this
caused CO2 concentrations > IDLH to exist in the restroom at
breathing zone height. Table VI provides data for IDLH grab
sampling completed at the frozen food production facility.
As at the brewery, airborne CO2 concentrations > 4% were
expected beforehand and SCBA respiratory protection was
used by the authors as needed to complete assessments in
hazardous locations.
Poultry Processing Facility
Chickens were killed, cleaned, and butchered at the poul-
try processing facility. The lack of local exhaust ventilation
allowed gases and vapors emitted within the plant to travel
throughout the facility, including locations where three FSIS
inspectors stood while examining chicken carcasses moving
through the evisceration room. The carcasses moved on an
overhead conveyor to other areas of the plant for further
processing in several dip tanks, and finally were cut as needed
to produce marketable products which were then packaged for
shipment.
Two visits occurred about two months apart, and CO2
was initially not a suspected stressor. Several real-time de-
tection tools were used, including the field-portable FTIR
instrument, to detect or rule out acetic acid and ammonia as
potential air contaminants. The spectral library used with the
FTIR instrument contained reference spectra for these ana-
lytes, and while no evidence was seen for their presence, ele-
vated CO2 concentrations were detected throughout the facility
(Table VII). Upon investigation, an employee was observed
826 Journal of Occupational and Environmental Hygiene
TABLE VII. Results for Grab Samples Collected
during First Visit to the Poultry Processing Plant:
Laboratory and Field FTIR Analyses
Field FTIR Laboratory
Analysis Analysis
Results Results
Sample Location/Time (% CO2 ) (% CO2 )
Evisceration room/9:05 amA 0.53 0.51
Evisceration room/1:15 pmA 0.53 0.51
Dip tank area/2:40 pmB 0.46 0.44
Icing room/2:05 pmB 1.25 1.08
Icing room/2:56 pmB 0.88 0.80
AGrab sample collected from the breathing zone of an FSIS inspector. BGrab
sample collected at chest height.
shoveling dry ice into boxes in the facility’s icing room. The
dry ice was kept in a large tote box, with no mechanical
ventilation present.
Dual port sampling pumps were not available for TWA CO2
sampling during the first visit, and an exhaust fan was added
to the icing room near floor level between the first and second
site visits. This likely resulted in lower CO2 concentrations
being measured in that area and in the evisceration room using
the handheld NDIR detector during the second visit, and field
FTIR and laboratory analysis results for personal 8-hr TWA
CO2 samples during the second visit are provided in Table
VIII. Laboratory analysis of these TWA samples did not show
that the FSIS employees working in the evisceration room
were overexposed to CO2 when sampled during the second
visit.
In 1988 Jacobs and Smith described elevated CO2 expo-
sures at four different poultry processing facilities.(17) Detector
tubes were used as a field screening tool, and Tedlar bags were
R
used for personal TWA sampling. Their data showed that CO2
was lost from the bags before analysis, as detector tube results
obtained with air from bags in the field were much higher than
the laboratory results. When evacuated steel canisters were
used to ship whole-air samples initially collected into bags,
measured 8-hr TWA CO2 concentrations for dry ice packaging
workers were in better agreement with field detector tube
results. Documentation for the OSHA sampling and analytical
method(10) describes the need to use a five-layer aluminized
bag to avoid sample losses similar to those described by these
authors.
Usefulness of CO2 Field-Detection Tools
Fast-responding real-time measurements identified condi-
tions at the brewery where IDLH conditions could be rapidly
attained, while 8-hr TWA sampling for CO2 failed to iden-
tify a hazard (Tables II and III). The 8-hr TWA sampling
at the frozen food production facility easily detected per-
sonal 8-hr TWA overexposures to airborne CO2 , however,
December 2015
 TABLE VIII. Laboratory Analysis Results for Personal 8-hr TWA Sampling of Poultry Plant FSIS Inspectors
for CO2 Exposure
Sample A 8-hr TWA CO2 B
Duration (min) Exposure Severity
Employee 1 201C 0.6
217D
Employee 2 217C 0.4
201D
Employee 3 214C 0.5
204D
ASeparate bags were used for both morning and afternoon sampling. B1.0 = 0.5% CO2 as 8-hr TWA; based on laboratory analysis results for both morning and
afternoon sampling with unsampled time counted as zero CO2 exposure. CMorning sample. DAfternoon sample.EMeasurement not taken.
fast-responding CO2 detection tools were still needed to deter-
mine that IDLH conditions were associated with certain tasks,
Downloaded by [152.180.134.66] at 07:45 04 November 2015
and the handheld NDIR detector allowed the path taken by the
CO2 gas detected in the restroom to be traced back through
the grated floor drain to CO2 use in the adjoining room. The
handheld NDIR detector also allowed the authors to identify
CO2 gas operation of pneumatic machinery, identifying 8-
hr TWA sampling of workers near the machinery as a high
priority.
Even though the large gas-phase FTIR instrument rapidly
produces concentration information, it is not particularly use-
ful as a fast-responding field detection tool. It requires stable
electrical power for operation and thus would mostly be used
at a fixed location, with whole-air samples brought to the
instrument. Also, this type of instrument is not as readily
available to most industrial hygienists as detector tubes or
a small handheld NDIR detector. However, the usefulness
of the FTIR instrument was demonstrated for the whole-air
FIGURE 5. Comparison between FTIR field analyses of various
gas bag samples with respective laboratory-determined CO2
concentrations up to 1.08% for the same whole-air samples.
The manufacturer-supplied reference spectra used for these FTIR
analyses ranged from 500–10,000 ppmv (0.05–1%) CO2 .
Journal of Occupational and Environmental Hygiene
Field FTIR Analysis Laboratory Analysis
Result (%CO2) Result (%CO2 )
0.35 0.33
0.35 0.33
0.25 0.22
0.26 0.24
0.26 0.24
—E 0.28
sample collected in the restroom of the frozen food production
facility, with the FTIR measuring airborne CO2 at 4.96% there
following the use of liquid CO2 in the adjoining kitchen (Table
VI). Confirmation through laboratory analysis was not possible
due to a damaged bag that leaked during shipment. The FTIR
reference spectra used during field analysis did not extend
to CO2 concentrations > 1.0%, but the instrument indicated
CO2 concentrations outside this range and results were re-
evaluated after creating additional reference spectra. Using
the laboratory-generated CO2 reference spectra after the fact,
a CO2 concentration value of 6.80% was obtained, which was
close to the concentration measured in real-time using the
handheld NDIR detector.
The detection of unexpectedly elevated CO2 concentra-
tions by FTIR spectroscopy in the poultry processing facility
demonstrated the ability of the FTIR instrument to detect
unexpected analytes and to produce quantitative results very
close to those obtained from the subsequent GC analysis of
corresponding whole-air samples in the laboratory. Only a
zero-point calibration of the FTIR instrument was completed
before use each day using either ultra-high purity N2 or helium,
and close agreement between the field FTIR analyses and those
completed on the same whole-air samples in the laboratory
was possible without the need for further field calibration.
A comparison between field FTIR and laboratory analysis
results that fell very close to or within the range of reference
spectra used for field analyses is provided in Figure 5 which
combines data from Tables V, VII, and VIII. The data were
highly correlated, and the slope of the resulting line was near
unity.
CONCLUSIONS
A irborne CO2 may migrate and its concentration can
rapidly increase when not controlled. A focus only on
TWA personal sampling may lead a health and safety profes-
sional to overlook IDLH conditions, and TWA sampling is
not sufficient in cases where such rapid increases may occur.
Tools such as detector tubes and an NDIR detector were found
December 2015 827
 to be effective to assess immediate airborne concentrations,
and to determine locations in compliance cases for collect-
ing both personal TWA and grab type whole-air samples for
laboratory analysis. Each tool provided different benefits and
disadvantages, with detector tubes being inexpensive, highly
portable, and easy to use. However, results were somewhat
subjective, and a finite supply of tubes and the need to focus
on preparing and using a tube were limitations. The NDIR
detector was highly portable and easy to use, providing nearly
instantaneous concentration readout. Limitations for the NDIR
detector included availability (cost), a finite battery life, and
the possible need to adjust readings for pressure and tem-
perature which affect the density of gas samples. The FTIR
spectroscopy instrument was found to be accurate in the field,
but with limitations of cost, portability (requiring a constant
line power source), the need for an experienced operator (e.g.,
for selection of wavenumber range for quantitation, and verifi-
cation that interfering analytes are not present), and the typical
need to collect a grab sample which then must be moved to
Downloaded by [152.180.134.66] at 07:45 04 November 2015
the stationary instrument for analysis.
Users must understand the limitations of available detection
tools to effectively monitor exposures. A full CO2 exposure
assessment for both TWA and potentially IDLH exposures
through 8-hr TWA sampling methods combined with fast-
responding CO2 detection tools may be needed to best address
worker health and safety.
DISCLAIMER
T he views expressed here are those of the authors. This
document is not a standard or regulation. It creates no
new legal obligations and alters no existing obligations created
by OSHA standards or the Occupational Safety and Health
Act. It may contain recommendations that are advisory in
nature, informational in content, and are intended to support
the provision of safe and healthful workplaces.This article is
not subject to U.S. copyright law.
REFERENCES
1. American Conference of Governmental Industrial Hygienists
(ACGIH): Carbon dioxide. In Documentation of the Threshold Limit
Values and Biological Exposure Indices, 7th ed. Cincinnati, OH: ACGIH
Worldwide, 2001.
828 Journal of Occupational and Environmental Hygiene
2. Ikeda, N., H. Takahashi, K. Umetsu, and T. Suzuki: The course of
respiration and circulation in death by carbon dioxide poisoning. Forensic
Sci. Int. 41:93–99 (1989).
3. Dripps, R.D., and J.H. Comroe Jr.: The respiratory and circulatory
response of normal man to inhalation of 7.6 and 10.4 per cent CO2 with
a comparison of the maximal ventilation produced by severe muscular
exercise, inhalation of CO2 and maximal voluntary hyperventilation. Am.
J. Physiol. 149:43–51 (1947).
4. Sieker, H.O., and J.B. Hickam: Carbon dioxide intoxication: the clinical
syndrome, its etiology and management with particular reference to the
use of mechanical respirators. Medicine 35:389–424 (1956).
5. Smith, P.A., B. Lockhart, B.A. Besser, and M.A.R. Michalski:
Exposure of unsuspecting workers to deadly atmospheres in below-
ground confined spaces and investigation of related whole-air sample
composition using adsorption gas chromatography. J. Occup. Environ.
Hyg. 11:800–808 (2014).
6. OSHA: “Occupational Safety and Health Standards, Subpart Z – Toxic
and Hazardous Substances” Code of Federal Regulations, Title 29, Part
1910.1000.
7. American Conference of Governmental Industrial Hygienists
(ACGIH): 2015 Threshold Limit Values for Chemical Substances and
Physical Agents and Biological Exposure Limits. Cincinnati, Ohio:
ACGIH Worldwide, 2015.
8. U.S. National Institute for Occupational Safety and Health (NIOSH):
NIOSH Pocket Guide to Chemical Hazards, Publication No. 2010-168c.
Cincinnati, OH, 2010.
9. “Occupational Safety and Health Standards, Subpart I – Respiratory
Protection,” Code of Federal Regulations, Title 29, Part 1910.134.
10. “Carbon Dioxide in Workplace Atmospheres: Method ID-172.” Available
at http://www.osha.gov/dts/sltc/methods/inorganic/id172/id172.html (ac-
cessed 20 August, 2014).
11. “Carbon Dioxide: Method 6603.” Available at http://www.cdc.gov/
niosh/docs/2003-154/pdfs/6603.pdf (accessed 20 August, 2014).
12. Heikkilä, A.: Field-Portable Fourier Transform Infrared (FTIR) Spec-
troscopy for Gas and Vapor Analysis, Chapter 8. In: Important Instru-
mentation and Methods for the Detection of Chemicals in the Field, P.A.
Smith, and G.W. Cook (eds.). Fairfax, VA: American Industrial Hygiene
Association, 2013. pp. 101–113.
13. Safety Equipment Institute, Inc. (SEI): “Safety Equipment Institute,
Inc. (SEI) – Certified Products.” Available at http://www.seinet.org/
search/search.php. [Accessed October 10, 2014.]
14. Roper, P.: The NIOSH detector tube certification program. Am. Ind. Hyg.
Assoc. J. 35:438–442 (1974).
15. American National Standards Institute (ANSI): American national
standard for gas detector tube units – short term type for toxic gases
and vapors in working environments (ANSI/ISEA 102-1990 (R2009))
[Standard]. Washington, D.C.: ANSI, 2009.
16. Riley, R.L., and B. Bromberger-Barnea: Monitoring exposure of
brewery workers to CO2 : a study of cellar workers and controls. Arch.
Environ. Health 34:92–96 (1979).
17. Jacobs, D.E., and M.E. Smith: Exposures to carbon dioxide in the
poultry processing industry. Am. Ind. Hyg. Assoc. J. 49:624–629 (1988).
December 2015