Designation: D7941/D7941M − 14

Standard Test Method for

Hydrogen Purity Analysis Using a Continuous Wave Cavity
Ring-Down Spectroscopy Analyzer1
This standard is issued under the fixed designation D7941/D7941M; the number immediately following the designation indicates the
year of original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last
reapproval. A superscript epsilon (´) indicates an editorial change since the last revision or reapproval.

1. Scope D7606 Practice for Sampling of High Pressure Hydrogen

1.1 This test method describes contaminant determination in and Related Fuel Cell Feed Gases
fuel-cell-grade hydrogen as specified in relevant ASTM and D7649 Test Method for Determination of Trace Carbon
ISO standards using cavity ring-down spectroscopy (CRDS). Dioxide, Argon, Nitrogen, Oxygen and Water in Hydrogen
This standard test method is for the measurement of one or Fuel by Jet Pulse Injection and Gas Chromatography/
multiple contaminants including, but not limited to, water Mass Spectrometer Analysis
(H2O), oxygen (O2), methane (CH4), carbon dioxide (CO2), D7653 Test Method for Determination of Trace Gaseous
carbon monoxide (CO), ammonia (NH3), and formaldehyde Contaminants in Hydrogen Fuel by Fourier Transform
(H2CO), henceforth referred to as “analyte.” Infrared (FTIR) Spectroscopy
2.2 ISO Standards:3
1.2 This test method applies to CRDS analyzers with one or ISO/DIS 14687-2 Hydrogen fuel—Product specification—
multiple sensor modules (see 3.3 for definition), each of which Part 2: Proton exchange membrane (PEM) fuel cell
is designed for a specific analyte. This test method describes applications for road vehicles
sampling apparatus design, operating procedures, and quality ISO/DIS 14687-3 Hydrogen fuel—Product Specification—
control procedures required to obtain the stated levels of Part 3: Proton exchange membrane (PEM) fuel cell
precision and accuracy. applications for stationary appliances
1.3 The values stated in either SI units or inch-pound units 2.3 U.S.-Specific Standards:
are to be regarded separately as standard. The values stated in SAE J2719-2011 (2011) Hydrogen Fuel Quality for Fuel
each system may not be exact equivalents; therefore, each Cell Vehicles4
system shall be used independently of the other. Combining 2.3.7 California Code of Regulations, Title 4, Division 9,
values from the two systems may result in non-conformance Chapter 6, Article 8, Sections 4180-4181 – Hydrogen fuel
with the standard. quality requirements5
1.4 This standard does not purport to address all of the Environmental Protection Agency 40 CFR: Protection of the
safety concerns, if any, associated with its use. It is the Environment, Appendix B to Part 136 – Definition and
responsibility of the user of this standard to establish appro- Procedure for the Determination of the Method Detection
priate safety and health practices and determine the applica- Limit6
bility of regulatory limitations prior to use.
3. Terminology
2. Referenced Documents 3.1 Definitions:
2.1 ASTM Standards: 2 3.1.1 For definitions of terms used in this test method, refer
D4150 Terminology Relating to Gaseous Fuels to Terminology D4150.
D5287 Practice for Automatic Sampling of Gaseous Fuels 3.2 Acronyms:
D7265 Specification for Hydrogen Thermophysical Property 3.2.1 AIST, n—National Institute of Advanced Industrial
Tables Science and Technology

1 3
This test method is under the jurisdiction of ASTM Committee D03 on Gaseous Available from International Organization for Standardization (ISO), 1, ch. de
Fuels and is the direct responsibility of Subcommittee D03.14 on Hydrogen and la Voie-Creuse, CP 56, CH-1211 Geneva 20, Switzerland, http://www.iso.org.
4
Fuel Cells. Available from SAE International (SAE), 400 Commonwealth Dr., Warrendale,
Current edition approved June 1, 2014. Published July 2014. DOI: 10.1520/ PA 15096-0001, http://www.sae.org.
5
D7941_D7941M-14 Available from the California Office of Administrative Law, 300 Capitol Mall,
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or Suite 1250, Sacramento, CA 95814, http://www.oal.ca.gov/ccr.htm.
6
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM Available from United States Environmental Protection Agency (EPA), William
Standards volume information, refer to the standard’s Document Summary page on Jefferson Clinton Bldg., 1200 Pennsylvania Ave., NW, Washington, DC 20004,
the ASTM website. http://www.epa.gov.

Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States

1
 D7941/D7941M − 14
3.2.2 CRDS, n—cavity ring-down spectroscopy and subsequent blockages that pose a safety risk or the
3.2.3 IR, n—infrared introduction of contaminants into the gas stream upon evapo-
ration of the liquid. Users are reminded to consult Practice
3.2.4 kPa, n—kilopascal
D7265 for critical thermophysical property such as the ortho/
3.2.5 LDL, n—lower detection limit para hydrogen spin isomer inversion that can lead to additional
3.2.6 MSDS, n—material safety data sheet hazards in liquid hydrogen usage. In addition to this test
3.2.7 NIST, n—National Institute of Standards and Technol- method employing CRDS, test methods such as D7649 (carbon
ogy dioxide, argon, nitrogen, oxygen and water) and D7653 (IR
active species) are used to measure impurities in hydrogen fuel.
3.2.8 NPL, n—National Physical Laboratory
3.2.9 ppb, n—parts per billion v/v 6. Apparatus
3.2.10 ppm, n—parts per million v/v 6.1 The analyzers used to measure impurities with reference
3.2.11 PTB, n—Physikalisch-Technische Bundesanstalt to the development of this test method are based on CRDS.
3.2.12 psig, n—pounds per square inch (gauge) CRDS is an optical spectroscopic technique that enables
measurement of absolute optical extinction by samples that
3.2.13 slpm, n—standard liters per minute
scatter and absorb light. Based upon the optical extinction or
3.2.14 v/v, n—volume/volume ratio “ring-down” rate, a determination of the analyte concentration
3.2.15 VCR, n—a type of compression gas fitting can be made. See Appendix X1 for a detailed explanation on
3.3 Additional Definitions—The “sensor module” consists the principles upon which CRDS is based.
of the optical system (CRDS mirrors, reference cell, one or 6.2 Measurement Sequence—
more lasers, and other optical components), the detector, and 6.2.1 A tunable laser emits a directed beam of light energy
the internal gas handling components (gas lines, filters, and through an ultra-high reflectivity mirror into the absorption cell
regulators). The complete instrument, including control (cavity). The sample gas passes through this cell either via the
electronics, can contain a single sensor module or multiple use of a vacuum pump for samples under 170 kPa [10 psig] or
sensor modules. under pressure from sources in excess of 170 kPa [10 psig],
regulated to between 170 and 960 kPa [10 and 125 psig].
4. Summary of Test Method 6.2.2 High sensitivity is attained by reflecting the laser light
4.1 This test method provides a procedure for the sampling many times through a sample gas contained between two
of trace contaminants contained in fuel-cell-grade hydrogen highly reflective mirrors; thereby, a path length as high as
and subsequent measurement using cavity ring-down spectros- many kilometers through the sample is obtained.
copy (CRDS). Instrument and sampling system configurations 6.2.3 A detector such as a photodiode senses the initial
for sample pressures ranging from ambient to high pressure photon flux at the output of the cavity. Once a preset level of
(defined as >960 kPa [>125 psig]) are described. light intensity is detected, the light source is shuttered or
diverted from the cavity, and the light intensity is measured
5. Significance and Use over time.
5.1 Proton exchange membranes (PEM) used in fuel cells 6.2.4 On each successive pass through the cell, a small
are susceptible to contamination from a number of species that amount of light or ring-down signal emits through the second
can be found in hydrogen. It is critical that these contaminants mirror and is measured by the photodiode detector.
be measured and verified to be present at or below the amounts 6.2.5 Once the light “rings down,” the detector achieves a
stated in SAE J2719, ISO 14687-2 and ISO 14687-3 to ensure point of zero light intensity within a few hundred microseconds
both fuel cell longevity and optimum efficiency. Contaminant and the measurement is complete.
concentrations as low as single-figure ppb for some species can 6.2.6 Two measurement sequences are required to effect a
seriously compromise the life span and efficiency of PEM fuel measurement of concentration:
cells. The presence of contaminants in fuel-cell-grade hydro- 6.2.6.1 On-peak Measurement—The laser is tuned to a
gen can, in some cases, have a permanent adverse impact on wavelength at which the analyte absorbs light. The wavelength
fuel cell efficiency and usability. It is critical to monitor the of choice depends on the analyte, the targeted concentration
concentration of key contaminants in hydrogen during the range, and potential interference from other molecules present
production phase through to delivery of the fuel to a fuel cell in the sample. Suitable wavelengths for certain molecule can
vehicle or other PEM fuel cell application. In ISO 14687-2 and commonly be determined by using spectroscopic databases
ISO 14687-3, the upper limits for the aforementioned contami- such as HITRAN. The exact wavelength used for each analyte
nants are specified. Refer to SAE J2719 and the California is generally considered a trade secret by the manufacturer.
Code of Regulations (see 2.3) for example specific national and 6.2.6.2 Off-peak Measurement—The laser is tuned to a
regional requirements. For hydrogen fuel that is transported wavelength at which the analyte does not absorb light. The
and delivered as a cryogenic liquid, there is additional risk of wavelength of choice depends on the analyte, the targeted
introducing impurities during transport and delivery opera- concentration range, and potential interference from other
tions. For instance, moisture can build up over time in liquid molecules present in the sample. As before, suitable wave-
transfer lines, critical control components, and long-term lengths can be determined by consulting spectroscopic data-
storage facilities, which can lead to icing up within the system bases such as HITRAN. The exact wavelength used for the

2
 D7941/D7941M − 14
off-peak measurement of each analyte is considered a trade 125 psig]. Samples with a pressure in excess of 960 kPa [125
secret by the manufacturer, but it is generally in close proxim- psig] shall be regulated down to a pressure acceptable for the
ity to the on-peak wavelength. In a gas of consistent analyte CRDS instrument before introduction to the inlet. Exceeding
concentration, an off-peak measurement is required only occa- the maximum allowable pressure may damage the instrument.
sionally; however, it is recommended that an off-peak mea- Consult the manufacturer for required sample pressure condi-
surement is performed at least once per month. In samples with tions. CRDS analyzers configured exclusively for use at
rapidly changing gas composition or analyte concentrations, an pressures above 170 kPa [10 psig] cannot be used for lower
off-peak measurement may be performed as frequently as pressure samples even with addition of a vacuum pump.
every few minutes. The frequency of off-peak measurement 9.1.2 Commonly available CRDS instruments contain ap-
does not affect the accuracy of the final measurement. propriate particle filtration inside the internal gas handling
6.2.7 The on-peak and off-peak measurements are used to components; further filtration is generally not required unless
calculate the concentration of the analyte in the sample gas as specified by the manufacturer for special analytes and sample
per a variation of the Beer-Lambert Law relating the extinction conditions
of light to the absorbance of the material through which the 9.1.3 To connect gas lines to the instrument, VCR fittings
light is travelling. are recommended. When making connections, always use a
6.3 Details concerning specific instrument configurations new gasket (nickel or stainless steel gaskets are recom-
for a range of sample pressures can be found in Section 9. mended).
9.1.4 For the measurement of most common analytes (e.g.
6.4 A full description of the CRDS technique can be found
H2O), sample lines and wetted components shall be of stainless
in Appendix X1.
steel construction, ideally with electro-polished surface finish,
7. Hazards free from particulate and other contamination such as oils and
other hydrocarbons. Certain analytes may require alternative
7.1 High-pressure gases. materials or surface treatments, or both, to optimize sampling
WARNING– Improper handling of compressed gas cylin- conditions. Contact an appropriate vendor for further advice.
ders containing air, hydrogen, or inert gases such as nitrogen or 9.1.5 Switching valves shall be constructed with a stainless
helium can result in explosion. Rapid release of hydrogen or steel diaphragm type and with the surface area of valves and
inert gases can result in asphyxiation. Hydrogen is a potential other wetted components kept to a minimum, avoiding any
fire hazard. Compressed air supports combustion. dead volume. Surface treatments for the wetted surfaces when
7.2 Hydrogen available to minimize the absorption of impurities. Contact an
7.2.1 Potential explosion hazard. appropriate vendor for further advice. Sample line length
7.2.2 Purge with inert gas before oxygen service. should be minimized and “dead-legs” avoided, preventing
diffusion of contamination from unswept surfaces. Refer to
8. Equipment, Materials, and Supplies Practices D5287 and D7606 for further sampling guidance.
8.1 Equipment— 9.1.6 Sampling Setup—A schematic of the sampling setup is
8.1.1 CRDS analyzer consisting of laser source(s), sample shown in Fig. 1.
cavity, photodiode detector, reference gas cell, and internal gas 9.2 Test Specimens—Test specimens may be samples of
handling components (gas lines, particle filters, and regulators fuel-cell-grade hydrogen ranging from ambient to high pres-
to maintain a constant pressure), which constitute each sensor sure with an instrument hardware and software configuration
module, as well as control electronics. defined accordingly. Additional pressure regulation will be
8.1.2 Electrical and fiber optic cables to connect the control required for samples exceeding the maximum allowed pressure
electronics and the laser source with each sensor module, if the (see 9.1.1). Refer to Practice D7606 for guidance on this
sensing modules are provided as separate units. matter.
8.1.3 Gas sample lines made from appropriate material
(stainless steel recommended) with a diameter of at least 6 mm 9.3 Method Blank—A CRDS instrument uses a spectro-
[0.25 in.] from the sample extraction point to the analyzer inlet scopic zero (see 6.2.6.2) to determine the measurement zero or
and the analyzer outlet to the vent or vacuum pump. baseline. A blank sample is therefore not required.
8.1.4 A vacuum pump for low pressure samples (see 9.1.1) 9.4 Test Units—The test unit considered for the preparation
which can reach a pressure of approximately 1 Torr or less. of this test method is a commonly available CRDS instrument.
8.2 Materials and Supplies—Dry inert gas (e.g. nitrogen or The configuration of the internal sampling system will vary
clean dry air) as purge gas for installation of the analyzer. depending on the available sample pressure.
9.5 Instrument and Analytes—The general setup of the
9. Sampling, Test Specimens, and Test Units CRDS instrument is independent of the analyte to be measured;
9.1 Sampling— however, some components of the sensor module such as the
9.1.1 For those CRDS instruments that can accept sample laser source and the cavity mirrors are specific to the analyte
pressures from ambient up to 960 kPa [125 psig], a vacuum and the measurement range specified by the manufacturer for
pump is required for sample pressures below 170 kPa [10 the particular sensor. A CRDS analyzer sensor module shall
psig]. The analyzer may be used in the absence of a vacuum only be used for the analyte and measurement range for which
pump for sample pressures between 170 and 960 kPa [10 and it was designed.

3
 D7941/D7941M − 14

FIG. 1 Typical Sampling Configuration; pump is omitted or bypassed for high pressure samples (>170 kPa) with the appropriate CRDS
analyzer

9.6 Operating Conditions—In general, exposure to severe 10.1.6 During and after installation—The sample gas inlet
weather conditions shall be avoided. The instrument is able to pressure shall be maintained within the instrument’s specifica-
tolerate typical ambient fluctuations of pressure and moderate tions (see 9.1.1).
changes in temperature (within operating limits). A typical 10.1.7 Assuming appropriate inlet pressure conditions (see
operating temperature range is between 10°C and 40°C with 9.1.1), remove the sample inlet cap and connect the sample line
non-condensing humidity conditions. Refer to the manufac- to an inert purge gas source or a switching valve that connects
turer specification for operating conditions of a specific CRDS to both the purge and sample gas. Use two wrenches to hold the
analyzer. fitting in place while tightening. Tighten the VCR fitting with
a new metal gasket and purge at least 15 minutes before
10. Preparation of Apparatus connecting to the sensor module.
NOTE 1—In addition to the procedure outlined in this section, consult 10.1.8 Assuming appropriate inlet pressure conditions (see
Practice D7606 for guidance on sampling high pressure hydrogen. In 9.1.1) and sufficient purge (see 10.1.7), remove the purge line
general, this procedure does not vary for different analytes; however, if the
sample contains high concentrations of a dangerous substance, appropriate from the instrument and connect the sample line to the sensor
safety precautions must be taken. Consult the analyte’s MSDS for module. With a new metal gasket, immediately connect the
guidance. sample line to the sensor module sample inlet and tighten the
10.1 Connecting the sample to the inlet: VCR fitting. If a switching valve is used, switch from the purge
10.1.1 The manual or factory should be consulted for to the sample gas.
appropriate sample lines and fittings, which may vary depend- 10.1.9 Save the sample inlet cap for future use.
ing on analyte. Sample lines shall be free of particulate or other 10.2 Connecting to the sample outlet:
contamination. 10.2.1 It is generally recommended that the instrument be
10.1.2 The manual or factory should be consulted for vented to atmospheric pressure. It can also be vented to a
recommended fittings, welds, and regulators. vacuum pump. The vent line shall consist of 6-mm [0.25-in.] or
10.1.3 Use the shortest possible connection from sample larger diameter tubing.
source to the analyzer inlet. 10.2.2 Careful consideration should be given when venting
10.1.4 To avoid contamination from ambient air, purge the H2 sample gas. Hydrogen is an asphyxiate and fire hazard.
sample line(s) before connecting to the sensor module. It is Also, consult local regulations for venting hydrogen. If the
advisable to have an arrangement whereby a manual or sample contains high concentrations of contaminants of dan-
automatic means of switching between the sample and an inert gerous substances, take appropriate safety measures. Consult
purge gas is available. The sampling system should be de- the MSDS for proper venting of the sample gas.
signed so as to minimize any unswept surfaces when either the 10.2.3 If the vent line is connected to a vacuum pump,
sample or purge line is not in use. ensure the pump line is closed before switching on the pump.
10.1.5 An internal particle filter is used and is intended to Ensure that the vacuum pump is certified for use with hydrogen
trap larger particles that may be introduced into the flow gas.
system during hookup. External particle filters may be con- 10.2.4 Assuming appropriate inlet pressure conditions (see
nected but will act as moisture traps and flow restrictions, 9.1.1), with a flow of 0.5 to 1.0 slpm, remove the sample outlet
resulting in long initial dry-downs and sluggish response. For cap from the sensor module. With a new metal gasket,
this particular instrument, a 2 µm particle size filter is recom- immediately connect the vent line to the sample outlet and
mended. tighten the VCR fitting.

4
 D7941/D7941M − 14
10.2.5 Open the line to atmosphere or a vacuum pump and 11.5.1 Non-interfering species—In any CRDS instrument,
allow 15 min to purge the sample lines. nitrogen, hydrogen, oxygen, and noble gases do not interfere
10.2.6 Save the sample outlet cap for future use. with the measurement regardless of their concentration. Inter-
ference testing for these species is therefore not required.
11. Calibration and Standardization 11.5.2 Samples and analytes for interference testing—For
interference testing, separate sample gas mixtures of 200 ppm
11.1 Calibration—CRDS analyzers are essentially “self- of CO2 in H2, 500 ppm of H2O in H2, and 100 ppm CH4 in H2
calibrating” with respect to the absorption measurement. Al- shall be prepared (100-times the expected highest concentra-
though calibration standards are used during manufacturing for tion in an SAE J2719 compliant hydrogen sample). The gas
the purpose of traceability, CRDS analyzers are based on mixtures shall contain as little as possible of the analyte(s) to
fundamental physical principles and do not require periodic be tested, but no more than allowed by SAE J2719 (see Table
recalibration. CRDS analyzers measure the time (typically in 1). The sample gases can be prepared as one mixture or
microseconds) for light to decay (“ring down”) inside an separate mixtures. Interference tests are to be performed for
optical cavity, typically consisting of two highly reflective each analyte measured by the CRDS instrument, either simul-
mirrors. The optical losses in the cavity reduce the amount of taneously or separately. Every analyte shall be tested for
light with each pass, allowing for the measurement of a interference with all prepared sample gas mixtures, unless one
“ring-down time.” When a number of target molecules are of them is the analyte itself (for example, if CO2 is the analyte,
present in the gas flowing through the cavity, they absorb light, interference testing for CO2 is obviously not applicable).
therefore shortening the ring-down time. A full description of 11.5.3 Negative readings—If the CRDS instrument has any
CRDS can be found in Appendix X1. In practice, the two setting that–if enabled–would prevent the analyzer from show-
critical parameters that shall be controlled are the laser ing negative concentration readings, this feature has to be
frequencies that correspond to a zero point (Tau Zero) and a disabled for the interference tests.
point of peak or maximum absorption (Tau Peak). These are 11.5.4 Settling and measurement times—After connecting
controlled as follows: each sample gas, allow for sufficient settling time to achieve
11.2 Reference cell—A commonly available CRDS instru- stable readings (typically 10 to 15 min). To obtain reliable
ment contains a spectroscopic reference cell that automatically measurement results, allow for at least 10 to 15 min of
re-centers the laser frequency during measurements to coincide measurement time. Longer settling and measurement times
with the analyte’s peak absorption frequency. The reference may be required for “sticky” molecules such as H2O.
cell itself is a small, permanently sealed container of the target 11.5.5 Determination of maximum interference bias—To
analyte. A very small percentage of the laser light is sent to the determine the maximum bias due to interference for analyte i,
reference cell, which continuously verifies that the laser follow these steps for each analyte:
remains at the correct wavelength, which does not change with 11.5.5.1 Calculate the mean concentration reading Cij of
ambient temperature or pressure. analyte i when run with sample j (with j being one of the three
sample gas mixtures of CO2, H2O, or CH4, described in
11.3 Tune—The tune-Tau Zero mode is used to determine
11.5.2).
the off-peak ring-down time of the system. This measurement
11.5.5.2 Calculate POS i 5Σ C ij for all Cij>0
is used in calculating the final concentration and is run in the j

same sample gas and under the same sample conditions as the and
analyte measurement itself. Running a tune-Tau Zero cycle at NEGi = Σ |C ij | for all Cij<0.
j
least every month is recommended to ensure accurate contami-
nant concentration. This may be done manually via the TABLE 1 Specifications
appropriate menu, or the process can be automated to a NOTE 1—Repeatability measured with different instruments with
designated schedule. For one manufacturer, the tune-Tau Zero separate, dedicated sensor modules for each analyte. Typical response
cycle runs for approximately two minutes during which time time to obtain results below is two to three minutes.
the instrument is not delivering measurement data. Contaminant/Analyte SAE J2719 Tested 3σ Tested repeatability
Detection detection (ppb) at mean con-
11.4 Laser optimization—Over time, the laser may drift off Limit (ppb) limit (ppb) centration level
the analyte’s absorption peak. The software adjusts the laser (ppb)
Water (H2O)A 5000 LR: 0.08 LR: 0.10 at 0.44
current to keep the laser “on peak.” Laser optimization is HR: 4.2 HR: 5.2 at 15 and
recommended at least once per year to ensure the unit is 20 at 996
operating optimally. Methane (CH4) 100 0.68 0.48 at 0.40
Carbon Monoxide (CO) 200 41 26 at 21
11.5 Avoidance of interferences—When multiple analytes Carbon Dioxide (CO2) 2000 161 92 at 81
Formaldehyde (H2CO) 10 6.1 5.5.at 5.5
are present in the sample, biased readings can occur due to Ammonia (NH3) 100 0.86 0.97 at 1.52
spectral interference. Before installation, the analyzer shall be Oxygen (O2) 5000 0.12 0.042 at 0.34
tested for common interferences to ensure correct concentra- A
HR (high range) and LR (low range) models use different absorption lines
tion readings.

5
 D7941/D7941M − 14
11.5.5.3 The maximum bias Bimax is then determined by 15. Report
B i
max 5 0.01 3 max$ P O S i , N E G i% (1) 15.1 Report sampling date and time, flow rate, sampling
. duration, and additional comments as necessary. Combine with
11.5.6 Insignificant interference—If Bimax is smaller than the relevant file containing the analyte concentration data.
the analyzer’s 3σ detection limit for analyte i, the interference 16. Detection Limits, Precision, Bias, and Linearity
bias is regarded as insignificant. 16.1 Test configurations for different analytes—A com-
11.5.7 Significant interference—If Bimax is larger than the monly available CRDS analyzer sensor module is generally
analyzer’s 3σ detection limit for analyte i, the interference bias configured according to Fig. 2. The sensor module possesses
is regarded as significant. In this case, the instrument or the the same general configuration for every analyte in Table 1;
measurement procedure for analyte i has to be modified however, laser wavelength and optical coatings are specific to
appropriately. After implementation of these modifications, each analyte. The sensor module can be configured as an
analyte i shall be re-tested for interference. integrated single-channel analyzer (sensor plus electronics) or
as a multi-channel instrument with multiple sensor modules
12. Conditioning
sharing one control unit. The sample is a mixture of the analyte
12.1 When the start-up procedure described in Section 9 has in H2, typically from a certified gas cylinder (62% accuracy).
been completed, as a final step, the system should be purged For H2O, a moisture generator is used to generate a known
with an inert gas for at least 15 minutes with a flow rate of 0.5 concentration of H2O.
to 1.0 slpm or until such time as the measured analyte 16.2 Detection limits—The detection limits for all mol-
concentration has stabilized. The time required to reach a ecules listed in Table 1 are based on the required detection limit
steady analyte concentration may be longer (shorter) with a stated in SAE J2719. The CRDS numbers are determined by
lower (higher) flow rate. experiment using the specific configuration following the
ASTM definition (i.e. dedicated sensor module per analyte).
13. Procedure The detection limit is specified as three times the standard
13.1 CRDS provides a continuous measurement of an ana- deviation (3σ) of the measured analyte concentration using a
lyte concentration in a given matrix gas. Measuring the analyte gas sample that contains no or extremely small amounts of the
concentration in a given sample is simply a matter of switching analyte.
between the purge gas and sample gas and allowing the 16.3 Precision—This standard has not yet undergone an
measurement reading to stabilize. To obtain correct concentra- interlaboratory study to substantiate the listed precision data.
tion readings, the appropriate gas matrix has to be selected in The statistical examination of the laboratory test results is as
the instrument software, in this case “Hydrogen.” Incorrect follows:
matrix gas selection may result in false concentration readings. 16.3.1 Repeatability—The difference between successive
test results obtained by the same operator with the same
14. Calculation or Interpretation of Results apparatus under constant operating conditions on identical test
14.1 As described in Section 11, a CRDS instrument pro- material would, in the long run, in the normal and correct
vides a direct, absolute reading of an analyte concentration in operation of the test method, exceed the following values by
a given gas sample for a specified concentration range. No only one case in twenty (experimental results are listed in Table
further interpretation is required. Measurement data may be 1).
accessed via download of a text file stored within the 16.3.2 Reproducibility—The difference between two single
instrument, or data may be collected real time via data export and independent results obtained by different operators work-
options such as analog output, RS-232, or Ethernet. ing in different laboratories on identical test material would, in

FIG. 2 Typical CRDS Configuration

6
 D7941/D7941M − 14
the long run, exceed the following values only in one case in 17.1.3 Employing a point-of-use purifier—If readings on the
twenty as to be determined in the interlaboratory study analyzer appear to be suspiciously high, a point-of-use purifier
(experimental results to be determined). for the analyte to be measured can be installed directly at the
16.4 Bias—Experimental results to be determined in the inlet of the analyzer. If the readings remain high after
forthcoming interlaboratory study. installation, the analyzer may be malfunctioning. A Cavity
Peak Scan may be performed as additional method of verifi-
16.5 Linearity—Due to its fundamental principles on which cation.
CRDS is based, a typical instrument exhibits a linearity 17.1.4 Cavity Peak Scan procedure—Instead of only mea-
coefficient of >0.995 over at least four orders of magnitude of suring on the peak of the absorption line of the analyte at a
concentrations. Fig. 3 shows test data of a typical instrument fixed laser temperature, the temperature can be varied in small
for trace O2 detection with different intrusion levels (step-up increments (typically 0.02°C increments within -3 °C to +1°C
and step-down pyramid) in the lower part of the dynamic around the normal operating temperature) to provide a scan of
range. The correlation between nominal and measured concen- the entire absorption line. One manufacturer of CRDS instru-
tration is 0.995 with a linearity coefficient (R2) of 0.9995 for ments provides this procedure as automated program. The
the step-up intrusion and 1.011 with an R2 of 0.9999 for the results of the scan along with the instrument’s displayed
step-down intrusion. reading are usually sent to the manufacturer who can verify
17. Validation and Quality Assurance/Control Procedures that the Cavity Peak Scan results match the displayed reading.
17.1 Validation— 17.2 Instrument Failure—A typical CRDS analyzer contains
17.1.1 Validation procedure using a certified cylinder— critical components which cause the instrument to not produce
Although CRDS instruments are accurate upon manufacture, data or to deliver inaccurate readings when they are compro-
improper installation of the gas sampling system may result in mised. Proper operation of these components is ensured via the
precise but inaccurate measurements. Upon initial installation following procedures:
of a new system, the CRDS readings shall be validated using a 17.2.1 Laser source—In case of a complete failure of the
cylinder standard, certified to 62% accuracy and containing laser source, there will be no light available for the measure-
concentrations in the range of 1 to 10 ppm for every analyte to ment system. The CRDS instrument monitors the light inten-
be monitored. To ensure long-term integrity of the measure- sity from the diode. If laser light is not detected, the instrument
ment results, the validation procedure may be repeated peri- will cease to measure and alert the user of the laser failure.
odically. Validation is recommended once per year. 17.2.2 Mirror reflectivity—Mechanical shock, extreme
17.1.2 Tampering with the calibration and suspicious temperatures, particulate matter or other contamination can
readings—If at any point analyzer measurements appear sus- change the reflectivity of the cavity mirrors. The instrument
pect or it appears the instrument’s calibration settings have provides a regular “tune” cycle (see 11.3) to adjust for changes
been tampered with, a point-of-use purifier for the analyte to be in mirror reflectivity. When analyzing clean and analytically
measured can be used (see 17.1.3). Alternatively, a Cavity Peak consistent samples such as most hydrogen fuel samples, the
Scan (see 17.1.4) can be performed to validate the accuracy of “tune” cycle should be run once a month. When analyzing
the instrument’s measurements without having to use a certi- potentially dirty sample or samples with variable sample gas
fied cylinder standard or a purifier. compositions, mechanical instability, or rapidly changing

FIG. 3 Pyramid Step Intrusion of Different Analyte Levels (O2) Using a Typical CRDS Trace Analyzer

7
 D7941/D7941M − 14
temperature, a “tune” is recommended more frequently. A pressurizing the instrument. For pressures requiring a vacuum
change in mirror reflectivity may affect the noise performance pump, proper operation of the pump has to be ensured. While
of the instrument (sensitivity and precision); however, mea- not required, monitoring the flow through the instrument using
surement accuracy is generally not affected. a calibrated mass flow meter at the sample outlet (or behind the
17.2.3 Electronic components—Any failure in electronic vacuum pump for low pressure samples) is recommended.
components will result in the instrument being non-functional;
therefore, a failure can easily be noted. 18. Keywords
17.3 Gas sampling system—The gas flow must be main- 18.1 absorption; absorption spectroscopy; Beer-Lambert
tained within the required specifications for both flow and law; infrared absorption; infrared analysis; IR absorption;
pressure (see 9.1.1) for instrument functionality and accurate laser; laser-based spectroscopy; near-infrared; NIR; PEM fuel
analyte measurement. If a pressurized sample is used, regula- cell; optical technique; tunable diode laser; quantum cascade
tors are to be set appropriately to ensure sufficient pressure to laser; cavity-enhanced spectroscopy; cavity ring-down spec-
achieve positive flow through the analyzer without over- troscopy; vehicle fuel

APPENDIX

(Nonmandatory Information)

X1. CAVITY RING-DOWN SPECTROSCOPY (CRDS)

X1.1 General Principle X1.3 On- and Off-peak Measurement

X1.1.1 CRDS is a form of optical absorption spectroscopy. X1.3.1 To measure the absorption of a specific analyte, the
It works by attuning the wavelength of laser light to the unique ring-down time both on the peak of the absorption and at a
molecular fingerprint of an analyte. The light and sample are “zero” wavelength, where the analyte does not absorb, is
contained in an optical cavity containing highly reflective compared. Typically, a tunable laser is used to change between
mirrors (typically R >99.99%) affixed to opposite ends of the on- and off-peak wavelengths. The on-peak measurement is
cell. By rapidly shutting off the laser firing into the cavity, the given by Eq X1.4. Off-peak, the ring-down time τ0 is only
light intensity built up inside the cavity will decay due to the determined by the mirror losses, hence:
residual transmission of the mirrors and the absorption of the 1 L
analyte. By comparing this decay time with a reference τ0 5 3 (X1.4)
c 12R
measurement performed at a wavelength where the analyte
does not absorb, the absorption characteristics of the analyte X1.4 Determination of Analyte Concentration
can be measured. X1.4.1 By comparing the on-peak ring-down time τ with the
off-peak ring-down time τ0, the number density of the analyte
X1.2 Relation to the Beer-Lambert Law NX is determined via
X1.2.1 The Beer-Lambert Law relates the extinction of light
to the absorption properties of a sample in the following way: Nx 5
1
σ xc S
3
1
τ
2
1
τ0 D (X1.5)

I ~ l ! 5 I 0 exp ~ 2 α l ! (X1.1) Here, σx is the known absorption cross-section of the analyte

at the chosen on-peak wavelength, typically obtained from a
where spectroscopic reference database (see X1.8.1). From the
I = intensity of the light after a path length through the number density, the relative concentration can be calculated
sample using the ideal gas law.
l = path length
I0 = original light intensity X1.5 Advantage of CRDS
α = absorption coefficient of the sample X1.5.1 Insensitivity to Intensity Noise—It is notable that Eq
In CRDS, the light intensity I0 is built up inside a cavity with X1.3-X1.5, which are used to determine the analyte
a fixed length L; therefore, the decaying intensity can also be concentration, do not contain the light intensities I or I0 in
regarded as a time-dependent decay, hence contrast to classic absorption spectroscopy. This means, that
CRDS is insensitive to laser intensity fluctuations, thus elimi-
I ~ t ! 5 I 0 exp~ 2 t ⁄ τ ! (X1.2) nating one typical noise source.
where τ is the characteristic “ring-down time” of the CRDS
system, which is given by X1.5.2 Sensitivity Enchancement—With the mirror reflec-
1 L
tivity R typically being very close to unity, the denominator in
τ5 3
c 1 2 R1αL
(X1.3) Eq X1.3 and X1.4 becomes very small, causing a massive
Here, we assume for simplicity that the refractive index of effective increase in the interaction length. In a CRDS system,
the sample is ≈1 and that there are no losses other than the this enhancement leads to an effective absorption path length of
analyte absorption and mirror losses. as much as 100 kilometers [62 miles].

8
 D7941/D7941M − 14
X1.6 Typical CRDS Setup until it is completely extinct. Measuring the light emitted
X1.6.1 The key components in Fig. 2 are as follows: through the end mirror reveals the exponential decay of the
intracavity intensity.
X1.6.2 Diode Laser—Emits coherent light. Although diode
lasers are typically used, any tunable laser source with suffi- X1.8 Key Points and Principles
cient quality may be coupled into the cavity. X1.8.1 The spectroscopic characteristics (line strength and
X1.6.3 Isolator—Prevents light feedback from interfering pressure broadening coefficient) of the analyte are fundamental
with the laser. physical properties and are permanently programmed into the
instrument by factory calibration using NIST traceable refer-
X1.6.4 Acousto-optic modulator (AOM)—Shuttering device ence standards. Any modifications implemented into the ana-
for the light source. The use of an AOM is exemplary; it may lyzer are based on acceptance by recognized authorities,
be replaced with an alternate device performing the same including the U.S. National Institute of Standards and Tech-
function, which is to rapidly shut off the light beam. Electri- nology (NIST), the National Physical Laboratory (NPL) in the
cally shuttering off the light source is also an alternate United Kingdom, the National Institute of Advanced Industrial
implementation. Science and Technology (AIST) in Japan.
X1.6.5 CRDS absorption cell—With highly reflective X1.8.2 The laser is selected to operate at the wavelength
mirrors, creates measurement cavity. required for the target analyte. One common method to ensure
X1.6.6 Photodiode—Detects and measures the light that long-term wavelength stability is an internal spectroscopic
intensity, as it leaves the absorption cell. verification standard, such as a reference cell, which contains a
X1.6.7 Trigger—Works in concert with the photo-diode and small amount of the target analyte, and can be an automatic
sends signal to the AOM or alternate shut-off device to start the feedback process to maintain the correct laser wavelength.
ring-down decay. X1.8.3 Periodic determination of τ0 ensures that any
changes to the mirror losses are cancelled out. Factory
X1.7 Ring-down/Exponential Decay prequalification of each unit assures the system is operating
X1.7.1 In Fig. X1.1, the concept of ring-down decay within within specification. It is recommended that a τ0 measurement
the cavity after the laser source is shuttered is shown. As the (called “tune”) is performed at least monthly, either manually
laser light bounces back and forth between the ultra-high or on an automated schedule. Additional “tune” cycles are
reflective mirrors, the analyte species absorbs the light energy recommended when changing sample gases, after the instru-
ment was turned off, and when the analyzer is moved to a
different location.
X1.8.4 The matrix gas hydrogen is transparent throughout
the wavelength range of the used tunable lasers and around the
absorption peaks of the analytes in particular. The gas matrices
(including H2) in the library of a CRDS analyzer have been
tested to ensure they do not absorb light at the same wave-
length as the target analyte. The correct matrix (here H2) has to
be selected from the library to allow for the correct calculation
of the concentration using the right pressure broadening
coefficient, which is pre-programmed into the instrument’s gas
matrix database.
X1.9 Results from a Previous Inter-laboratory Study
X1.9 During an inter-laboratory study involving the metrology
institutes NIST, NPL, PTB, and AIST, the reproducibility
standard deviation was determined to be better than 62% of
the reading or the tested LDL (whichever was greater) and that
the 95% reproducibility limit was determined to be better than
64% of the reading or two times the tested LDL (whichever
was greater) for the analysis of moisture in N2. Similar results
FIG. X1.1 Ring-Down Decay within the Cavity after the Laser are expected in the inter-laboratory study for any of the listed
Source is Shuttered analytes in hydrogen.

9
 D7941/D7941M − 14
ASTM International takes no position respecting the validity of any patent rights asserted in connection with any item mentioned
in this standard. Users of this standard are expressly advised that determination of the validity of any such patent rights, and the risk
of infringement of such rights, are entirely their own responsibility.

This standard is subject to revision at any time by the responsible technical committee and must be reviewed every five years and
if not revised, either reapproved or withdrawn. Your comments are invited either for revision of this standard or for additional standards
and should be addressed to ASTM International Headquarters. Your comments will receive careful consideration at a meeting of the
responsible technical committee, which you may attend. If you feel that your comments have not received a fair hearing you should
make your views known to the ASTM Committee on Standards, at the address shown below.

This standard is copyrighted by ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959,
United States. Individual reprints (single or multiple copies) of this standard may be obtained by contacting ASTM at the above
address or at 610-832-9585 (phone), 610-832-9555 (fax), or service@astm.org (e-mail); or through the ASTM website
(www.astm.org). Permission rights to photocopy the standard may also be secured from the Copyright Clearance Center, 222
Rosewood Drive, Danvers, MA 01923, Tel: (978) 646-2600; http://www.copyright.com/

10