This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles

for the
Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.

Designation: D8470 − 22

Standard Practice for

Development and Implementation of Instrument
Performance Tests for Use on Multivariate Online, At-Line
and Laboratory Spectroscopic Based Analyzer Systems1
This standard is issued under the fixed designation D8470; 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 calibrations via Practice D8321 to establish the performance

1.1 This practice covers basic procedures that can be used to
develop instrument performance tests for spectroscopic based
online, at-line, laboratory and field analyzers. The practice is
intended to be applicable to Raman spectrometers and to
infrared spectrophotometers operating in the near-infrared and
mid-infrared regions.
1.2 This practice is not intended as a replacement for
specific practices, such as Practices E275, E925, E932, E958,
E1421, or E1683 that exist for measuring performance of
specific types of laboratory spectroscopic instruments. Instead,
this practice is intended to provide guidelines as to how similar
practices should be developed when specific practices do not
exist for a particular instrument type, or when specific practices
are not applicable due to sampling or safety concerns. This
practice can be used to develop instrument performance tests
for on-line process spectroscopic-based analyzers.
1.2.1 The performance tests described in this practice typi-
cally only evaluate the performance of the infrared spectropho-
tometer or Raman spectrometer part of the analyzer system,
referred to herein as the instrument.
1.2.2 Instrument performance tests do not typically evaluate
performance of analyzer sampling systems.
1.3 This practice describes univariate level zero and level
one tests, and multivariate level A and level B tests which can
be implemented to measure instrument performance. These
tests are designed to be used as rapid, routine checks of
instrument performance. They are designed to uncover mal-
functions or other changes in instrument operation, but do not
specifically diagnose or quantitatively assess the malfunction
or change. The tests are not intended for the comparison of
instruments or analyzers of different manufacture.
1.4 The instrument performance tests described in this
practice are used during the development of multivariate
1
This practice is under the jurisdiction of ASTM Committee D02 on Petroleum
Products, Liquid Fuels, and Lubricants and is the direct responsibility of Subcom-
mittee D02.25 on Performance Assessment and Validation of Process Stream
Analyzer Systems.
Current edition approved July 1, 2022. Published August 2022. DOI: 10.1520/
D8470-22.
level at the time the calibration is developed. The same tests are
used during validation of analyzers via Practice D6122 to
qualify the working analyzer by demonstrating comparable
performance.
1.4.1 Instrument performance tests are used to requalify
instruments after analyzer maintenance.
1.4.2 Instrument performance tests are used to qualify
instruments in secondary analyzers to which calibrations are
being transferred after development on a primary analyzer.
1.5 This standard does not purport to address all of the
safety concerns, if any, associated with its use. It is the
responsibility of the user of this standard to establish appro-
priate safety, health, and environmental practices and deter-
mine the applicability of regulatory limitations prior to use.
1.6 This international standard was developed in accor-
dance with internationally recognized principles on standard-
ization established in the Decision on Principles for the
Development of International Standards, Guides and Recom-
mendations issued by the World Trade Organization Technical
Barriers to Trade (TBT) Committee.
2. Referenced Documents
2.1 ASTM Standards:2
D4175 Terminology Relating to Petroleum Products, Liquid
Fuels, and Lubricants
D6122 Practice for Validation of the Performance of Multi-
variate Online, At-Line, Field and Laboratory Infrared
Spectrophotometer, and Raman Spectrometer Based Ana-
lyzer Systems
D7940 Practice for Analysis of Liquefied Natural Gas
(LNG) by Fiber-Coupled Raman Spectroscopy
D8321 Practice for Development and Validation of Multi-
variate Analyses for Use in Predicting Properties of
Petroleum Products, Liquid Fuels, and Lubricants based
on Spectroscopic Measurements
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
Standards volume information, refer to the standard’s Document Summary page on
the ASTM website.

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

1
 D8470 − 22
D8340 Practice for Performance-Based Qualification of
Spectroscopic Analyzer Systems
E131 Terminology Relating to Molecular Spectroscopy
E275 Practice for Describing and Measuring Performance of
Ultraviolet and Visible Spectrophotometers
E925 Practice for Monitoring the Calibration of Ultraviolet-
Visible Spectrophotometers whose Spectral Bandwidth
does not Exceed 2 nm
E932 Practice for Describing and Measuring Performance of
Dispersive Infrared Spectrometers
E958 Practice for Estimation of the Spectral Bandwidth of
Ultraviolet-Visible Spectrophotometers
E1421 Practice for Describing and Measuring Performance
of Fourier Transform Mid-Infrared (FT-MIR) Spectrom-
eters: Level Zero and Level One Tests
E1683 Practice for Testing the Performance of Scanning
Raman Spectrometers
E1840 Guide for Raman Shift Standards for Spectrometer
Calibration
E1866 Guide for Establishing Spectrophotometer Perfor-
mance Tests
3. Terminology
3.1 For terminology related to molecular spectroscopic
methods, refer to Terminology E131. For terminology relating
to petroleum products, liquid fuels and lubricants, refer to
Terminology D4175.
3.2 Definitions:
3.2.1 absorbance (A), n—the logarithm to the base 10 of the
reciprocal of the transmittance, (T).
A 5 log10~ 1 ⁄ T ! 5 2log10T
E131
3.2.1.1 Discussion—Absorbance is a measure of the capac-
ity of a substance to absorb light of a specific wavelength.
3.2.2 action limit, n—for multivariate spectroscopic analyz-
ers used in the analysis of liquid petroleum products and fuels,
the limiting value from an instrument performance test, beyond
which the multivariate spectroscopic analyzer is expected to
produce potentially invalid results. D6122
3.2.3 calibration, n—in multivariate spectroscopic
measurement, a process for creating a multivariate model
relating component concentrations or sample properties to
spectra for a set of known samples, referred to as calibration
samples. D8321
3.2.4 control limits, n—limits on a control chart that are
used as criteria for signaling the need for action or for judging
whether a set of data does or does not indicate a state of
statistical control.
3.2.5 extractive sampling, n—for spectroscopic process
analyzers used in the analysis of liquid petroleum products and
fuels, the process of transporting a sample from the process,
performing any necessary sample conditioning and finally
presenting the sample to the analyzer so as to produce a
spectrum of the process sample.
3.2.6 in situ sampling, n—for spectroscopic process analyz-
ers used in the analysis of liquid petroleum products and fuels,
the process of transporting light from the analyzer to a sample
2
probe located in the process wherein the light interacts with a
process sample, and collecting the transmitted or scattered
light, returning it to the analyzer where it is analyzed by the
instrument to produce a spectrum of the process sample.
3.2.6.1 Discussion—For some NIR and nearly all Raman
analyzers, the light will typically be transported to and from the
analyzer using fiber optics.
3.2.7 instrument, n—for spectroscopic analyzers used in
petrochemical service, the spectrometer or spectrophotometer,
associated electronics and computer, spectrometer or spectro-
photometer cell, and if utilized, transfer optics. D6122
3.2.8 instrument performance verification sample, n—for
multivariate spectroscopic analyzers used in the analysis of
liquid petroleum products and fuels which employ extractive
sampling, a material representative of the product being
analyzed which is adequately stored in sufficient quantity to be
used as a check on instrument performance; instrument perfor-
mance verification samples are used in instrument performance
tests and as checks on calibration transfer, but the samples and
their spectra are generally not reproducible long term D6122
3.2.8.1 Discussion—In E1866 and previous versions of
D6122 and this practice, an instrument performance verifica-
tion sample was referred to as a test sample.
3.2.9 instrument qualification sample, n—for multivariate
spectroscopic analyzers used in the analysis of liquid petro-
leum products and fuels, a single pure compound, or a known,
reproducible mixture of compounds whose spectrum is con-
stant over time such that it can be used in an instrument
performance test. D6122
3.2.9.1 Discussion—In E1866 and previous versions of
D6122 and this practice, an instrument qualification sample
was referred to as a check sample.
3.2.10 level A test, n—for spectroscopic analyzers used in
the analysis of liquid petroleum products and fuels, a pass/fail
instrument performance test in which the spectrum of a check
or instrument performance verification sample is compared
against historical spectra of the same sample via a multivariate
analysis.
3.2.11 level B test, n—for spectroscopic analyzers used in
the analysis of liquid petroleum products and fuels, a pass/fail
instrument performance test in which the spectrum of a check
or instrument performance verification sample is analyzed
using a multivariate model, and the results of the analysis are
compared to historical results for prior analyses of the same
sample.
3.2.12 level one (1) test, n—for spectroscopic analyzers
used in the analysis of liquid petroleum products and fuels, a
simple series of measurements designed to provide quantitative
data on various aspects of spectrophotometer performance and
information on which to base the diagnosis of problems.
3.2.13 level zero (0) test, n—for spectroscopic analyzers
used in the analysis of liquid petroleum products and fuels, a
routine check of instrument performance, which can be done in
a few minutes, designed to visually detect significant changes
in instrument performance and provide a database to determine
instrument performance over time.
 D8470 − 22
3.2.14 liquid petroleum products and fuels, n—in relation to
analyzers, any single-phase liquid material that is produced at
a facility in the petroleum and petrochemical industries and
will be in whole or in part of a petroleum product; it is
inclusive of biofuels, renewable fuels, blendstocks, alternative
blendstocks, and additives. D8340
3.2.15 model variables, n—the independent variables de-
rived from the calibration spectra which are regressed against
the calibration sample properties to produce the multivariate
model. D6122
3.2.15.1 Discussion—For MLR, the model variables would
be the spectral intensity at the selected wavelengths or frequen-
cies; for PCR or PLS, the model variables are the Principal
Components or latent variables.
3.2.16 optical reference material, n—for spectroscopic ana-
lyzers used in the analysis of liquid petroleum products and
fuels, an optical filter or other device which can be inserted into
the optical path in the spectrometer, spectrophotometer or
probe producing a spectrum which is known to be constant
over time such that it can be used in place of a check or
instrument performance verification sample in a performance
test.
3.2.17 primary analyzer, n—the analyzer(s) on which cali-
bration spectra are collected for the purpose of building a
multivariate model. D8321
3.2.18 Raman Shift Standard, n—a physical sample having
known Raman shift characteristics used to determine the
operating wavelength of laser module and correct for any
short-term or accumulated error. The position of the spectra
band(s) of this material can be used to calculate the operational
wavelength of the laser:
1
λi 5 (1)
S v̄ 1
1
λs D 5. Test Conditions
where λi is the incident wavelength (the operational wave-
length of the laser) in cm, λs is the measured wavelength of
the Raman band in cm, and v̄ is the accepted standard posi-
tion of the Raman band of the reference material in
wavenumbers. D7940
3.2.19 secondary analyzer, n—an analyzer not used in the
development of the multivariate model, but which will be used
for analysis of new materials. D8321
3.2.20 spectral intensity, n—a generic term referring to
either infrared absorbance or Raman scattering intensity.
D8321
3.2.21 spectral position, n—a generic term referring to
either wavelength or frequency position in a spectrum. D8321
3.2.22 Spectrum Standard, n—light source of known spec-
trum used to standardize/calibrate the detection module and
providing correct mapping of scattered wavelength to physical
pixel coordinates/location. Typically, an atomic emission
source such as a neon lamp is used for this purpose. D7940
4. Significance and Use
4.1 If ASTM Committee E13 has not specified an appropri-
ate test procedure for a specific type of instrument, or if the
sample specified by a Committee E13 procedure is incompat-
3
ible with the intended instrument operation, then this practice
can be used to develop practical performance tests.
4.1.1 For instruments which are equipped with permanent
or semi-permanent sampling accessories, the test sample speci-
fied in a Committee E13 practice may not be compatible with
the instrument configuration. For example, for FT-MIR instru-
ments equipped with transmittance or IRS flow cells, tests
based on putting polystyrene films into the sample position are
impractical. In such cases, this practice suggests means by
which the recommended test procedures can be modified by
changing the test material or the location of the recommended
test material.
4.1.2 For instruments used in process measurements, the
choice of test materials may be limited due to process
contamination and safety considerations. The practice suggests
means of developing performance tests based on materials
which are compatible with the intended use of the analyzer.
4.2 Tests developed using the practice are intended to allow
the user to compare the performance of an instrument on any
given day with prior performance, and specifically to compare
performance during calibration of the analyzer to performance
during validation of the analyzer and during routine use of the
analyzer. The tests are intended to uncover malfunctions or
other changes in instrument operation, but they are not de-
signed to diagnose or quantitatively assess the malfunction or
change. The tests are not intended for the comparison of
analyzers of different manufacture.
4.3 Tests developed using this practice are also intended to
allow the user to compare the performance of a primary
analyzer used in development of a multivariate model to the
performance of secondary analyzers used to apply that model
for the analysis of process or product samples.
5.1 When conducting the performance tests, the instrument
should be operated under the same conditions as will be in
effect during its intended use. Sufficient warm-up time should
be allowed before the commencement of any measurements.
5.1.1 If possible, the optical configuration used for measure-
ments of instrument performance verification and instrument
qualification samples should be identical to that used for
normal operations. If identical optical configurations are not
possible, the user should recognize that the performance tests
may not measure the performance of the entire instrument.
5.1.2 Data collection and computation conditions should
generally be identical to those used in normal operation.
However, instrument performance tests can use data collection
and computation conditions that are more demanding than
those used in normal operation if advantageous for instrument
standardization.
5.1.3 Spectral data used in performance tests should be date
and time stamped, and the results of the tests should be stored
in a historical database.
6. Materials Used for Performance Testing
6.1 The types of materials used for performance testing will
vary depending on whether the analyzer uses extractive or in
situ sampling.
 D8470 − 22
6.1.1 For analyzers using extractive sampling, it is generally
possible to introduce an instrument qualification or instrument
performance verification sample into the transmission/
scattering cell. The materials used for performance testing are
chosen to be compatible with the instrument configuration, and
to provide spectral features which are adequate for the tests
being performed.
6.1.1.1 A liquid sample used for performance testing will
generally be in the same physical state (gas, liquid, or solid) as
the samples to be analyzed during normal operation of the
instrument.
6.1.1.2 A liquid sample used for performance testing should
be physically and chemically compatible with the samples
analyzed during normal operation so as to not represent a
safety or product quality issue if it ends up mixed into the
process stream being analyzed.
6.1.1.3 A liquid sample used for performance testing pref-
erably has a spectrum that is similar to the spectra which will
be collected during normal operation.
6.1.1.4 For infrared systems, a liquid sample used for
performance testing will preferably have several significant
absorbances (0.3 < absorbance < 1.0) across the spectral range
used for normal operation of the instrument.
6.1.1.5 In order to adequately determine the photometric
linearity of the infrared instrument, the peak absorbance for at
least one absorption band of a liquid sample will preferably be
similar to or slightly greater than the largest absorbance
expected for samples measured during normal operation.
6.1.1.6 A liquid sample used for performance testing will
typically be introduced directly into the transmission/scattering
cell and not pass through any sample conditioning system. As
such, it only tests the performance of the instrument and not the
total analyzer system.
6.1.2 For infrared analyzers using extractive sampling, in-
strument performance tests can be conducted by inserting an
optical reference material into the optical path when the
transmission cell is empty.
6.2 For analyzers using in situ sampling, introducing an
instrument qualification sample or an instrument performance
verification sample into the actual process sample probe can
only be done if the probe is removed from the process. For
analyzers equipped with optical multiplexers, a separate chan-
nel and probe may be used for the performance test. The
performance test can be conducted on an instrument qualifica-
tion sample, an instrument performance verification sample, or
on an optical reference material. It should be recognized that
such tests do not verify the performance of the actual process
probe.
6.3 Instrument Qualification Samples—Instrument qualifi-
cation samples can be used to conduct performance tests.
Instrument qualification samples are single pure compounds or
mixtures of compounds of definite composition.
6.3.1 Instrument qualification samples are used to conduct
Level A tests (see 9.1).
6.3.2 If mixtures are utilized as instrument qualification
samples, they must be prepared in a repeatable manner and, if
stored, stored such that the mixture is stable over long periods
of time. In preparing mixtures, components should be accu-
4
rately pipetted or weighed at ambient temperature. It is
recommended that mixtures be independently verified for
composition prior to use.
6.3.3 While mixtures can be used as instrument qualifica-
tion samples, their spectra may be adversely affected by
temperature-sensitive interactions that may manifest them-
selves by wavelength (frequency) and spectral intensity
changes.
6.4 Instrument Performance Verification Samples—An in-
strument performance verification sample is a process or
product sample or a mixture of process or product samples
whose spectrum is expected to be constant for the time period
it is used in performance testing. The instrument performance
verification sample must be stored in bulk quantities in
controlled conditions such that the material is stable over time.
6.4.1 Instrument Performance Verification Samples are used
to conduct Level B Test (see 9.2).
6.4.2 Since instrument performance verification samples are
often complex mixtures which cannot be synthetically
reproduced, they can only be used for performance testing for
limited time periods. If instrument performance verification
samples are used for this purpose, collection of historical data
on a new instrument performance verification sample should be
initiated before previous instrument performance verification
samples are depleted. It is recommended that new instrument
performance verification samples be analyzed sequentially
with old instrument performance verification samples at least
15 times before they are used to replace the old instrument
performance verification sample. The 15 analyses must be
performed over a time period that does not exceed one month
in duration.
6.5 Optical Reference Materials—An optical reference ma-
terial produces a spectrum which is known to be constant over
time. This material may be automatically inserted into the
optical path either within the instrument or in the fiber optic
sample probe to allow instrument performance tests to be
performed.
6.5.1 If an optical reference material is used routinely to
check or correct the spectral data collection or computation,
then the same material is preferably not used for instrument
performance testing. If the same filter is used, then the part of
the filter spectrum used in the performance testing should
preferably differ from that part used to check or correct the
instrument. For example, polystyrene filters are used to stan-
dardize (continuously check and correct) the wavelength scale
of some dispersive NIR spectrophotometers and Raman ana-
lyzers. For such systems, polystyrene filters are preferably not
to be employed for wavelength stability performance testing. If
polystyrene filters are used, then the peaks used for wavelength
stability testing should be different from those used for
standardizing the wavelength scale.
6.6 Spectrum Standards and Raman Shift Standards—Light
sources with known spectra are used for standardizing and
calibrating the frequency axis of Raman spectrometers. Atomic
emission sources such as neon lamps are used for this purpose.
The peak positions of a Raman Shift Standard such as toluene
can be used in instrument performance testing (Practice
 D8470 − 22
D7940). Practice E1840 lists various materials that can be used
as Raman shift standards.
6.7 For Raman systems, the spectral features used in per-
formance testing should be in the linear range for the detector,
above the noise level but below the saturation level. If the
linear range of the Raman detector has not previously been
established, a series of mixtures should be measured at various
exposure times to determine the range over which response is
linear.
7. Univariate Measures of Absorbance
Spectrophotometer Performance
7.1 Energy Level Tests—Energy level tests are intended to
detect changes in the radiant power in the instrument beam.
Decreases in energy levels may be associated with deteriora-
tion of the instrument source, with contamination or misalign-
ment of optical surfaces in the light path, or with malfunctions
of the detector.
7.1.1 For single beam instruments where background and
sample spectra are measured separately at different times,
energy level tests are generally conducted on a background
spectrum. For double beam instruments where the ratio of
background and sample beam intensities is measured directly,
energy levels can be measured if it is possible to block the
sample beam.
7.1.2 Energy levels should be measured at a minimum of
two fixed frequencies (wavelengths). The frequencies (wave-
lengths) at which energy levels are measured should be chosen
to avoid interferences due to atmospheric components (for
example, absorptions of water vapor and carbon dioxide) and
from interferences due to optical components (for example,
OH absorptions in SiO2 cells and fibers). Preferably, regions
where the background spectrum is relatively flat and slowly
varying should be used for this test.
7.1.3 To minimize the effects of photometric noise on the
energy level measurement, it is preferable to average the
energy over a narrow frequency (wavelength) window.
Typically, the intensity at five points centered on the test
frequency are averaged.
7.2 Photometric Noise Tests—Photometric noise is mea-
sured at the same frequencies (wavelengths) used for the
energy level tests. Preferably, photometric noise tests are
conducted on a 100 % line spectrum. Alternatively, photomet-
ric noise tests may be conducted on the spectrum of an
instrument qualification or instrument performance verification
sample at regions where the spectrum is relatively flat, and the
sample spectral intensity is minimal (<0.1).
7.2.1 For single beam instruments where background and
sample spectra are measured separately at different times, a
100 % line spectrum is obtained by ratioing two successive
background measurements to obtain a transmittance spectrum.
If, during normal operation of the instrument, backgrounds are
collected with a reference material in the optical path, then this
same configuration should be used for performance testing.
Photometric noise calculations are preferably done directly on
the transmittance spectrum. Alternatively, the transmittance
5
spectrum may be converted to an absorption spectrum by
taking the negative log10 before the photometric noise calcu-
lations.
7.2.2 For double beam instruments, a 100 % line spectrum
is measured when the two beams are both empty, both contain
empty matched cells, or both contain reference samples in
matched cells.
7.2.3 Photometric noise is measured by fitting a line to the
spectrum over a short spectral region centered on the test
frequency (wavelength). The region should contain at least 11
data points, preferably contains 101 data points, and should not
exceed 2 % of the spectral range. The line is subtracted from
the spectral data, and the RMS noise is calculated as the square
root of the mean square residual.
7.2.3.1 If Ti is the transmittance at the frequency vi, then the
slope, m, and intercept, b, of a line through the n data points
centered at test frequency v0 are given by the following:
nΣiT i 2 ΣT i Σi ΣiT i
m5 5 (2)
nΣi 2 2 ~ Σi ! 2 Σi 2
Σi 2 ΣT i 2 ΣiΣiT i ΣT i
b5
nΣi 2 2 ~ Σi ! 2
5
n
(3)
The photometric noise is calculated as follows:
Noise RMS 5 Œ Σ ~ T i 2 ~ mi 1 b !! 2
n22
(4)
The index i in Eq 2-4 runs from – (n – 1)/2 to (n – 1)/2 (n
must be odd). The intercept represents the transmittance at test
frequency v0.
7.2.3.2 If photometric noise is calculated on spectra, the
spectral intensity values, Ai, are used in place of the transmit-
tance values, Ti, in Eq 2-4. If the abscissa for the spectral data
is wavelength, then wavelength values, λi, are used in place of
the frequency values, vi, in Eq 2-4. Calculations should be
consistently performed on the same data types.
7.2.4 Increases in the photometric noise can indicate a
misalignment of optical components, a source malfunction, or
a malfunction in the detector or electronics.
7.3 Short Term Baseline Stability Test—The transmittance is
monitored at each of the test frequencies (wavelengths) used in
the energy level and photometric noise tests. The intercept
calculated in Eq 3 represents the transmittance averaged over
the n points around test frequency v0. Deviation from 100 %
transmittance is an indication of short-term baseline instability
and may indicate a malfunction of the instrument.
7.3.1 If the tests are conducted on absorbance spectra,
deviations from zero absorbance is used as an indication of
baseline instability.
7.3.2 If photometric noise tests are conducted on the spec-
trum of an instrument qualification or instrument performance
verification sample, then variations in the absorbance spectrum
at the test frequencies are taken as an indication of short-term
baseline instability.
7.4 Optical Contamination Tests—The single beam back-
ground scan which was used for the energy tests is examined
for absorptions which might indicate contamination of optical
surfaces in the beam path.
 D8470 − 22
7.4.1 Failure to clean cell or probe windows, IRS surfaces,
etc., are the most common source of optical contamination.
Frequencies (wavelengths) at which typical samples exhibit
maximum absorbance should generally be examined. For
example, for systems used in hydrocarbon analysis, the regions
where the C-H stretching vibrations occur should be examined.
Significant increases above a nominal background level may
indicate contamination of windows and surfaces.
7.4.2 Instrument optical surfaces can be contaminated by
impurities in purge gases. For systems equipped with flow cells
or circulating liquid temperature control, leaks in connecting
lines can expose an optical surface to contamination. Users
should consider possible sources of contamination and deter-
mine appropriate frequencies at which absorptions would
result.
7.5 Purge Contamination Tests—For instruments which are
purged to minimize absorptions due to atmospheric
components, the single beam spectrum used for energy tests
should be checked for variations in purge quality. Frequencies
(wavelengths) at which potential contaminants absorb should
be identified, as should baseline points where contaminant
absorption would be minimal. The absorbance for contami-
nants is calculated as the negative log10 of the ratio of the peak
intensity to the baseline intensity.
7.6 Frequency (Wavelength) Stability Tests—Frequency
(wavelength) stability tests are conducted by monitoring the
peak positions of several peaks across the absorption spectrum
of the instrument qualification or instrument performance
verification sample or optical filter. At least three peaks are
used for the test. If possible, the peaks should be in the upper,
middle, and lower third of the spectral range.
7.6.1 The absorption for peaks used in this test are prefer-
ably in the range from 0.37 to 0.75. For peak absorptions
outside this range, the wavelength stability measurement may
show greater sensitivity to photometric noise.
7.6.2 Peaks used for the frequency stability test are prefer-
ably symmetric in shape and well resolved from neighboring
peaks. If such peaks are not available in the spectrum of the
instrument qualification/instrument performance verification
sample or optical material, the user should be aware that
changes in instrument resolution will affect the measured peak
position.
7.6.3 It is recommended that the peak position be deter-
mined by the following steps:
7.6.3.1 Compute the first derivative of the spectrum by
applying the appropriate digital filter to the spectrum. A
commonly used filter has been defined by Savitzky and Golay
(1)3 with corrections by Steiner, Termonia, and Deltour (2),
with application criteria discussed by Willson and Polo (3). The
latter reference discusses optimum filter parameters based upon
the relationship between spectral bandwidth and digitization
interval. A cubic filter is recommended. The number of points
used in the filter should be the quotient of the full-width-at-
3
The boldface numbers in parentheses refer to a list of references at the end of
this standard.
6
half-maximum (FWHM) of the peak being measured divided
by the digital resolution and rounded up to the nearest odd
integer.
7.6.3.2 Identify the zero-crossing associated with the peak
absorbance and compute its location by linear interpolation
between the two adjacent points straddling the zero crossing.
The zero crossing is taken as a measure of the peak position.
NOTE 1—Other peak finding algorithms can be used provided that they
accurately track peak position. The procedure described in Annex A1
should be used to test peak finding algorithms to determine if they are
appropriate for this application. It is the user’s responsibility to demon-
strate that the peak finding algorithm is appropriate for monitoring
instrument frequency (wavelength) stability.
7.7 Resolution Stability Tests—The resolution stability of
the instrument is monitored by measuring the bandwidths of
several absorption peaks in the spectrum of the instrument
qualification/instrument performance verification sample or
optical filter. At least three peaks are used for the test. If
possible, the peaks should be in the upper, middle and lower
third of the spectral range. Variations in the measured band-
widths are taken as an indication that the optical resolution of
the instrument is varying, suggesting a malfunction.
7.7.1 The spectral intensities for peaks used in this test are
preferably in the range from 0.37 to 0.75. For peak spectral
intensity outside this range, the resolution stability measure-
ment may show increased sensitivity to photometric noise.
7.7.2 Peaks used for the resolution stability test are prefer-
ably symmetric in shape and well resolved from neighboring
peaks. If such peaks are not available in the spectrum of the
instrument qualification/instrument performance verification
sample or optical filter, the results of the resolution stability test
may be variable.
7.7.3 It is recommended that the peak bandwidth be deter-
mined by the following steps:
7.7.3.1 Compute the second derivative of the spectrum by
applying the appropriate digital filter to the spectrum. A
commonly used filter has been defined by Savitzky and Golay
(1) with corrections by Steiner, Termonia, and Deltour (2), with
application criteria discussed by Willson and Polo (3). The
latter reference discusses optimum filter parameters based upon
the relationship between spectral bandwidth and digitization
interval. A cubic filter is recommended. The number of points
used in the filter should be the quotient of the FWHM of the
peak being measured divided by the digital resolution and
rounded up to the nearest odd integer.
7.7.3.2 Identify the zero crossing on each side of the peak
intensity and compute their locations by linear interpolation
between the two adjacent points straddling the zero crossings.
The difference in the frequencies of the interpolated zero
crossings is taken as a measure of the peak bandwidth.
7.8 Photometric Linearity Tests—Linearity of the instru-
ment response is important for quantitative applications.
Unfortunately, the absolute photometric linearity cannot be
checked in a quick performance test. To do so would generally
require the use of multiple standards of known absorbance. The
test described here is intended only to measure changes in the
photometric linearity of a instrument.
 D8470 − 22
7.8.1 Photometric linearity is tested using the ratio of the
spectral intensity of two or more peaks in the - spectrum. One
peak should have a spectral intensity at or near the maximum
spectral intensity that will be used for normal operations. The
other peaks are preferably less intense than this maximum. If
only two peaks are used, the second peak should be approxi-
mately half the intensity of the first peak.
7.8.2 Linear baselines for each peak are calculated from
points of minimal spectral intensity on opposite sides of the
peaks. The maximum spectral intensity for each peak is
corrected for the baseline, and the ratio of the spectral
intensities for the two peaks is calculated. The ratio is used to
track changes in the photometric linearity.
8. Univariate Measures of Raman Spectrophotometer
Performance
8.1 During the development of the analytic method, corre-
lations are established between spectra and the sample species
by taking spectra of known samples. Because of the inherent
linearity of the Raman effect, the method will correctly
measure sample concentrations if the Raman spectra are valid.
Thus, the primary task to ensure analyzer calibration is to
ensure the spectra are calibrated and standardized before the
analyzer is commissioned. There also needs to be a means to
ensure this calibration remains valid over time by using
instrument qualification approaches. A spectrum is essentially a
two-dimensional chart with the number of detected photons on
the vertical or intensity axis and the wavelength of those
photons on the horizontal axis. The mathematical method used
to generate analytic results from the spectra relies on knowing
FIG. 1 Example Neon Spectrum
7
the wavelength positions and relative intensities of the various
spectral features associated with the components. Each of these
axes is calibrated by optical means.
8.2 Wavelength Axis—For the wavelength axis calibration to
be standardized, and thus to know which detected vibration
frequencies correspond to given spectrum features, it is neces-
sary to determine the wavelength falling on each group of CCD
pixels. This is done by exposing the detector to light that is
comprised of known individual wavelengths. Typically, this is
done by arranging for light from a neon bulb to be periodically
and automatically imaged onto the detector. The emission
spectra of neon is comprised of a large number of individual
wavelengths that are known to great precision, and the physics
associated with neon light ensure wavelength stability through
time and over a wide range of environmental conditions, thus
establishing standardization. By recording where each neon
wavelength falls on the CCD, a map can be generated relating
pixel to wavelength. Any changes in the position of a given
wavelength on the detector as a result of thermal or mechanical
effects can thus be corrected by measuring the change with the
neon spectra. Ongoing instrument qualification is done analo-
gously.
8.2.1 Example Neon Spectrum—Y-axis: counts, X-axis: Ra-
man shift (cm-1) (see Fig. 1).
8.3 Intensity Axis Calibration—Optical Path Wavelength
Transmission Effıciency—The detection efficiency of signal
photons traveling from the sample, through the probe optics,
through the fiber, and finally, to the detection module, varies
with wavelength. Thus, different molecular vibrations have
 D8470 − 22
different detection efficiencies. These efficiencies are unique to
each instrument. Thus, for a method to be valid and accurate,
these variations shall be corrected to yield accurate relative
abundance calculations. During the system installation process,
just before commissioning, reference light with a known
intensity versus wavelength profile is transmitted through the
entire optical path by exposing it to the probe collection
aperture. A spectrum is taken of this light source, which is then
divided by the known profile, and the result is then stored as a
reference spectrum on the instrument being fabricated. This
reference spectrum is then used to correct subsequent sample
spectra to obtain spectra that are independent of the spectro-
graph throughput. There are several ways to produce this
reference light.
8.3.1 Broadband Light from Incandescent Bulb—The light
source is typically a tungsten halogen bulb with an integral
diffuser to ensure uniform illumination, driven by constant
current electronics to ensure stable operation. The bulb is
typically calibrated relative to a National Metrology Institute
(NMI) traceable reference source such as National Institute of
Standards and Technology (NIST) thus creating a table of
values relating the radiative intensity of the bulb/diffuser
combination at each wavelength over the spectral range of the
analyzer. The bulb/diffuser combination is presented to the
collection aperture of the probe and calibration spectra are
taken as described above. The bulb must be recertified at the
factory on a yearly basis. This is the preferred approach for
performing intensity calibration.
8.3.2 Fluorescent Material—A number of materials readily
fluoresce when illuminated by laser light producing a broad-
band light that has a known spectral profile. NIST produces
several types of glass doped with dyes that are specifically
engineered to calibrate Raman instruments. The glass is
presented to the active probe beam and a reference spectrum is
taken as described above.
8.3.3 Raman Spectra of Reference Material—Instead of a
broadband light source, the Raman spectrum of a known mix
of materials can be used as a reference. The mix should contain
each of the materials, in gravimetrically established
percentages, that are intended to be measured during analyzer
operation. The relative intensity of each band in the reference
spectrum will be established by the known Raman signature of
the material and its known molar percentage of the mix.
8.3.4 Spectra from Alternative Sources—Although not used
for intensity axis calibration and standardization, the same light
source used for wavelength calibration and standardization can
be used to validate the intensity axis. For example, each time
a neon spectrum is collected, a series of ratios of the individual
peaks is calculated. The most robust practice is to generate a
ratio of each peak with respect to other peaks being used for the
calibration (typically, this is eight to ten peaks). A set of these
ratio values are then stored on the analyzer during commis-
sioning to be used as an instrument qualification reference.
8.4 Ongoing and Field Calibration/Instrument
Qualification—As presented in 8.2, the wavelength axis is
calibrated and automatically validated periodically. Similarly,
the intensity axis can be validated by periodically exposing the
probe to one of the reference light source options covered in
8
8.3.1 – 8.3.4. This is typically done annually or at a convenient
time when the sample point is out of service. In some cases, it
is desired to check the intensity axis calibration without
removing the probe from its stream mounting. This can be
accommodated by considering that the system components that
can affect intensity calibration are the probe, the fiber-optic
cables, and the detection module. The detection module can be
checked for any changes in intensity calibration by comparing
the ratios of neon peak heights as discussed in 8.3.4. Note that
this is done automatically and periodically. The fiber-optic
cable and the probe are passive optical devices that are not
subject to wear or aging absent external modification or
contamination and, thus, do not require ongoing instrument
qualification. Any change that could affect intensity calibration
is typically caused either by contamination of the probe
window or fiber connections, or physical damage of the fiber or
probe. Either of these two scenarios would produce noticeable
effects in the Raman spectra that can be detected and acted
upon. The two most likely effects are a large drop in signal or
a large rise in the baseline background of the spectra, or both.
9. Multivariate Measures of Instrument Performance
9.1 Level A Tests—A Level A performance test is a pass/fail
test that is sensitive to many of the univariate performance
parameters discussed in Section 7. Level A tests do not identify
specific failure modes, but merely indicate if the instrument
performance is within historical bounds. In this test, the
spectrum of an instrument qualification sample, an instrument
performance verification sample or an optical filter is compared
to a historical spectrum of the instrument qualification sample,
the instrument performance verification sample or the optical
filter by multivariate methods (least squares fitting or a
PCR/PLS model; see Practice D8321 for descriptions of PCR
and PLS). This procedure can provide some information about
specific instrument parameters, but essentially looks for devia-
tions in the residual spectrum as compared to the historical
residual spectra.
9.1.1 Level A tests are generally applied on instruments
which are in use for multivariate, quantitative analysis. The
spectral range used in Level A tests should be comparable to
that used in the calibration model for the analysis being
performed. If the spectrum of the instrument qualification
sample, the instrument performance verification sample or the
optical filter used in the Level A test contains absorptions that
are significantly higher than those of the typical samples being
analyzed, then these peaks can be excluded from the Level A
fit.
9.1.2 Level A Tests Using a Least Squares Method:
9.1.2.1 In this Level A test, a least squares fit of the current
spectrum of the instrument qualification sample, instrument
performance verification sample or optical filter is conducted
against a historical spectrum of the same material. Baseline
terms may be included in the fit to compensate for variations in
baseline, and scaling may be applied to compensate for
pathlength variations. The types of compensations (baseline or
pathlength) used in the fit should be similar to those employed

in the multivariate model used for the actual analyzer measure-
ment. Methodology for calculating the least square fit is
discussed by Blackburn (4) and by Antoon, Koenig, and
Koenig (5).
9.1.2.2 A typical least squares model could be as follows:
g 5 a h h1a λ λ1a 1 11e
where:
g = column vector containing the current spectrum of the
instrument qualification sample, the instrument perfor-
mance verification sample or the optical filter,
h = column vector containing the historical spectrum of the
instrument qualification sample, the instrument perfor-
mance verification sample or the optical filter,
λ = (v for frequency-based spectra), column vector of the
wavelength axis values for spectra g and h,
1 = column vector of ones,
ah = coefficient for scaling the historical spectrum to match
the current spectrum,
aλ = coefficient which scales λ to provide a baseline correc-
tion which is linear in wavelength (or frequency),
a1 = coefficient for a baseline offset, and
e = the error in the fit.
The column vectors h, λ, and 1 are combined into a matrix
H, and the coefficients into a matrix A.
g 5 @h λ 1# FG
ah
aλ
a1
1e 5 HA1e
9.1.2.3 The estimated coefficients â are first determined by
linear least squares.
â 5 H 1 g 5 ~ H t H ! 21 H t g
9.1.2.4 The coefficients are then used to estimate the spec-
trum of the current sample ĝ.
ĝ 5 Hâ
9.1.2.5 The residuals from the fit are the difference between
the measured and estimated values for the data points, g – ĝ.
The residuals from the fit are squared and summed. The
resulting measure, herein referred to as the spectral residual, is
used as a measure of changes in the instrument performance.
This spectral residual should be plotted on control charts.
NOTE 2—Any function of the sum of the squares of the residuals can be
used, for example, the square root, or the square root of the sum divided
by the number of points.
9.1.2.6 Additionally, the scaling and baseline coefficients
can be monitored as an additional measure of instrument
performance.
9.1.3 Level A Tests Using a PCR or PLS Method—To
perform a Level A test using PCR or PLS, one must first
develop an appropriate model. A series of historical spectra for
the instrument qualification/instrument performance verifica-
tion sample, or the optical filter are analyzed by a PCR or PLS
regression algorithm using 100 % for the compositional value
to generate the Level A model. Generally, only one model
variable should be retained in the model since all the spectra
are of the same material. The type of pre- or postprocessing
D8470 − 22
done in the Level A test model should be comparable to that
done in the multivariate calibration models being used on the
instrument.
NOTE 3—Chemometricians might refer to the analysis described in
9.1.3 as principal component analysis rather than principal components
regression. However, the object here is to allow the Level A test to be
(5)
developed and applied using the same chemometric software employed in
the development and application of the multivariate calibration model.
9.1.3.1 The PCR or PLS model is used to analyze the
current spectrum of the instrument qualification/instrument
performance verification or optical filter. The estimate for the
current spectrum is generated. The spectral residuals are
calculated as the difference between the current spectrum and
its estimate. The spectral residual can be charted to determine
if the instrument is operating within historical specifications.
9.1.3.2 PCR and PLS models can also provide information
on the scaling of the current spectrum. For simple models,
variation in the estimated composition from 100 % is an
indication of scaling variation.
9.2 Level B Tests—Level B performance tests analyze the
spectrum of an instrument qualification sample, an instrument
performance verification sample or an optical filter against
multivariate models that are employed during the normal use of
the analyzer system. As such, Level B tests cannot be per-
formed during the multivariate calibration of a analyzer. Level
(6)
B tests monitor the instrument performance for deviations to
which a calibration model is sensitive. Tests on a limited
number of samples are not rigorous, but failures in these tests
are indicative that the instrument operation has changed.
9.2.1 The spectrum of the instrument qualification sample,
the instrument performance verification sample or the optical
(7) filter is analyzed using the multivariate model used during
normal instrument operation. The predicted value (property or
component concentration), the Mahalanobis distance, and the
spectral residuals are again compared to historical values to
(8) detect any change in the analyzer performance.
10. Performance Test Charts
10.1 Performance test results should be plotted on charts
and examined for trends. Such trend analysis may provide
early warnings of possible analyzer problems.
10.2 Statistical quality control charting methods (for
example, individual value control charts, exponentially
weighted moving average control charts, and moving range of
two control charts) can be used to detect statistically significant
changes in instrument performance. However, the statistical
control limits associated with these charts will not necessarily
be useful in judging the performance test results. Instead, some
performance test results are typically compared to action limits
as described in Section 10.
10.2.1 For some performance tests, the test results are
expected to trend continuously in one direction until such time
as the analyzer is serviced. For example, the energy output of
an infrared source is expected to decrease continuously as the
source ages, until such time as the source is cleaned or
replaced. The decreased energy may be observed as an increase
in the Level 0 photometric noise, or as an increase in the Level
A spectral residual. The daily change in energy, noise or
9
 D8470 − 22
residual may be large relative to the precision with which these
values can be measured but have tolerable effect on the
instrument results for the intended application. For such tests,
control charts and statistically derived limits may be inappro-
priate. An action limit for such tests needs to be determined
from historical data or simulations as discussed in Section 10.
10.2.2 For some performance tests, the test results are
expected to vary randomly about a fixed point. For example,
for a properly operating instrument, the Level 0 wavelength
value might be expected to vary randomly about some average
value. For such tests, the statistical control charts and control
limits can be usefully employed to set initial action limits in the
absence of historical data. Such initial action limits may be
loosened if statistically significant performance changes de-
tected by the control charts are not found to have significant
effect on the instrument results for the intended application.
10.2.3 Since, for instruments used in multivariate analyses,
Level B composition or property results for instrument quali-
fication or instrument performance verification samples are
most directly comparable to actual analyzer results, the Level
B composition or property estimates are most amenable to
statistical control charting. Action limits for Level B compo-
sition or property estimates can be set to statistically deter-
mined control limits.
11. Performance Test Action Limits
11.1 Spectroscopic analyses differ greatly in their sensitivity
to various aspects of instrument performance, and each appli-
cation differs in what constitutes an acceptable tolerance to
changes in the results caused by variations in instrument
performance. Although instrument performance tests are useful
in their own right, the user must be concerned with how
changes in the instrument performance affect results during
normal operation. Historical databases or simulations that
define acceptable performance for one application may not be
appropriate for another application. In addition, the level of
performance required by quantitative applications may be
changed by the updating of the calibration.
11.2 Setting Action Limits Based on Historical Data for
Performance Tests:
11.2.1 Performance tests provide quantitative measures of
instrument performance. These measures can be compared to
historical data for the same tests in order to recognize changes
of instrument performance. If historical data exist, limits for
each test can be set and the performance can be judged against
these limits. If historical data does not exist, it will be
necessary to collect them as a standard part of the instrument
operation, and such collection will eventually allow perfor-
mance limits to be established. The collection of the historical
database for performance tests should be an integral part of the
instrument operation and be continued for the life of the
instrument.
11.2.2 For instruments used in qualitative analysis, what
constitutes acceptable instrument performance may be difficult
to quantify. The expert analyst may only know that the spectra
“look wrong.” If a change in instrument performance is
detected, spectra of known (instrument qualification or instru-
ment performance verification sample) materials can be
10
collected, and the analyst can examine the spectra to determine
if the observed change in performance would distort the spectra
sufficiently to cause misidentifications to occur.
11.2.3 If the normal operation of the instrument involves the
use of spectral library searching or discriminative analysis for
materials identification or classification, then known (instru-
ment qualification or instrument performance verification
sample) materials should be reanalyzed whenever a change in
performance is detected to determine if the change reduces the
discrimination power of the analysis.
11.2.4 If the normal operation of the instruments involves
quantitative analysis, then quality assurance for the quantita-
tive analysis should be part of the normal operation. The
significance of changes in instrument performance are judged
by their effects on the quality control results for the normal
analysis.
11.2.4.1 If the quantitative method used during normal
operation is a primary method (for example, univariate cali-
bration against quantitatively prepared or certified standards),
then the quality control for the quantitative method will
generally involve measurement of a standard and comparison
of the results against the known value.
11.2.4.2 If the quantitative method used during normal
operation is a secondary method (for example, univariate or
multivariate calibration against results obtained by another
primary analytical method), then the quality control for the
quantitative method will generally involve periodic analyses of
an unknown by both methods and statistical comparison of the
results.
11.2.4.3 If the quantitative method used during normal
operation is within statistical quality control, then the results
for the performance tests conducted during the same time
period should be considered an example of acceptable instru-
ment performance and added to the historical database.
11.2.4.4 If the quantitative method used during normal
operation is not within statistical quality control, the results
from the performance tests may be examples of unacceptable
instrument performance, particularly if the results from the
performance tests are inconsistent with the historical database.
Examples of unacceptable instrument performance can be used
to set action limits for future performance tests.
11.2.4.5 It is strongly recommended that, at the time the
quantitative method is developed, spectra of the instrument
qualification sample, the instrument performance verification
sample or the optical filter be collected along with spectra used
for calibration. Performance tests can be applied to this data to
determine the level of performance at the time of calibration
11.2.4.6 Changes in analyzer performance that are detected
by Level 0 tests may or may not produce a significant change
in the results during normal operation. Different types of
quantitative analyses differ significantly in their sensitivity to
various aspects of analyzer performance. By plotting the Level
0 test results with the quality control results for the quantitative
method on control charts, conditions that lead to invalid
quantitative results can be identified, and action limits for each
Level 0 test can eventually be established.
11.2.4.7 For instruments where normal operation involves
use of a multivariate calibration model, increases in the
 D8470 − 22
spectral residuals that are detected by Level A tests will
generally reflect some change in the quantitative results pro-
duced by the instrument. Even if the analysis result does not
change, the spectral residuals measured as part of the outlier
testing will generally be expected to increase. The level of
increase that can be tolerated can be determined by plotting the
Level A test spectral residuals against analyzer results and
determining the maximum level at which valid analysis results
are produced.
11.2.4.8 For instruments where normal operation involves
use of a multivariate calibration model, changes in the values
produced by a Level B test are the most straightforward to
interpret since the values are directly comparable to the
analysis results. If the analysis of the spectrum of the instru-
ment qualification sample, the instrument performance verifi-
cation sample, or the optical filter is an interpolation of the
model, then limits can be set directly based on the desired
performance of the analyzer. If the analysis of the spectrum of
the instrument qualification sample, the instrument perfor-
mance verification sample or the optical filter is an extrapola-
tion of the model, then some care must be exercised in setting
limits since the extrapolated result may be more sensitive to
small changes in instrument performance than analyses that are
interpolations of the model. This is known as leverage. In this
case, initial limits should be confirmed by plotting the Level B
results against analysis results and determining the levels at
which valid analysis results are produced.
NOTE 4—Any one instrument performance verification sample, instru-
ment qualification sample, or optical filter only tests a small portion of the
multivariate model space and may not be sensitive to all aspects of
instrument performance. The Level 0, A, and B tests are intended to detect
possible instrument failure modes. Acceptable performance as measured
by Level 0, A and B tests is necessary but not sufficient by themselves for
demonstrating valid instrument performance. Comparison of analysis
results to in control, primary method laboratory values is also necessary to
demonstrate the validity of analysis results.
11.3 Determining Performance Action Limits by Simulating
Instrument Response Changes:
11.3.1 For instruments where normal operation involves use
of a multivariate calibration model, an alternative procedure
for determining action limits for instrument performance tests
is to take actual, diverse, but representative spectra that are
predicted well by the model, and to mathematically modify
11
these spectra to simulate the expected variations in the instru-
ment performance. The model sensitivity, for example, the
change in the results per unit change in a performance
parameter, can be estimated, and used to establish action limits
for each performance parameter based on the error tolerance
for the application. Instrument performance parameters which
can be modeled include wavelength (frequency) shifts, base-
line shifts, changes in photometric noise, resolution changes,
and detector linearity changes. The importance of different
performance parameters is both application and instrument
type dependent. Historical data for Level 0 performance tests
are the best practice to the type response changes that should be
modeled for a given instrument type.
11.3.1.1 For example, the sensitivity of an analyzer to
baseline drift can be simulated by adding various baselines to
a set of representative spectra, analyzing these spectra with the
calibration model, and determining the change in the results as
a function of the added baseline. The added baseline can, for
example, be parameterized in terms of offset, slope and
curvature so that the effects of each can be determined.
11.3.1.2 For example, the sensitivity of an analyzer to
wavelength (frequency) shift can be simulated by shifting the
wavelength (frequency) of a set of representative spectra (see
Annex A1), analyzing these spectra with the calibration model,
and determining the change in the results as a function of the
shift. If the shift is accomplished via interpolation of the
spectra, care must be exercised that the interpolation function
does not smooth or deresolve the spectra.
11.3.2 Changes in instrument performance seldom effect
only one aspect of that performance. If simulations are used to
set action limits for performance tests, it is essential that
multiple performance parameters by varied simultaneously.
The magnitude of the changes to the performance parameters
that should be simulated are best obtained from examination of
historical data on Level 0 performance tests conducted on the
type of instrument being tested.
12. Keywords
12.1 infrared spectroscopy; instrument performance; level
0; molecular spectrophotometer; near-infrared; process ana-
lyzer; Raman; spectrophotometer performance tests
 D8470 − 22

ANNEX

(Mandatory Information)

A1. PROCEDURE FOR TESTING PEAK FINDING ALGORITHMS

A1.1 Interpolation of Test Spectrum
A1.1.1 To test a peak finding algorithm, it is necessary to
interpolate and shift a test spectrum by amounts equivalent to
a fraction of the digital resolution of the spectrum. The
following procedure can be used to interpolate and shift the
spectrum.
A1.1.1.1 Four adjacent points in the spectrum are selected.
The points are numbered –1, 0, 1, and 2. The spectral intensity
at the four points is fit to a cubic equation.
A2 1 2 4 8 C2
points at each end) is treated as point 0 once. The values
Ai(i = 0.2, 0.4, 0.6 and 0.8) calculated for the repetitive
application of the filter are collected into 4 spectral vectors.
These vectors are assigned the same frequency scales as the
original spectrum. If ∆ is the digital resolution (data point
spacing), then the vectors A0.8, A0.6, A0.4, and A0.2 generated by
repetitive application of the above procedure represent spectra
which are shifted by –0.2∆, –0.4∆, –0.6∆, and – 0.8∆, respec-
tively.
NOTE A1.1—If the data points are numbered –1, 0, 1, and 2 from left to

3 43
A1
A0
A 21
43 45
1 1
1 0
1 21
1 1
0 0
1 21
C1
C0
C 21
↔A 5 XC (A1.1)
right, the interpolation estimates a value for the spectrum between point 0
and point 1. The original point at 0 is replaced with this estimate. The
effect is to shift the spectrum toward the left (negative index) direction.

C2 0 0 6 0 A2 A1.2 The peak finding algorithm is applied to the original

3 43
C 5 X 21 A↔
43 4C1
C0
C 21
21 6 23 22
0 3 26 3
1 23 3 21
A1
A0
A 21
and shifted spectra. The peak positions for suitable peaks are
calculated.
A1.2.1 If the peak positions calculated by the peak finding
(A1.2) algorithm for the shifted spectra are shifted by –0.2∆, –0.4∆,
A1.1.2 The cubic equation is evaluated at four intermediate –0.6∆, and –0.8∆, respectively, relative to the peaks for the
points: original spectrum, then the peak finding algorithm can be used
A 0.8 1 0.8 0.64 0.512 C2 for tracking frequency (wavelength) stability.

3 43
A 0.6
A 0.4
A 0.2
5
1
1
1
0.6
0.4
0.2
0.36
0.16
0.04
0.216
0.064
0.008
43 4 C1
C0
C 21
(A1.3) A1.2.2 If the peak positions calculated by the peak finding
algorithm for the shifted spectra are not shifted by –0.2∆,
–0.4∆, –0.6∆, and –0.8∆, respectively, relative to the peaks for
A1.1.3 The procedure is repeated, moving the filter side- the original spectrum, then the peak finding algorithm cannot
ways so that each point in the spectrum (other than the two be used for tracking frequency (wavelength) stability.

REFERENCES

(1) Savitzky, A. and Golay, M. J. E., “Smoothing and Differentiation of
Data by Simplified Least Squares Procedures,” Analytical Chemistry,
Vol 36, pp. 1627–1639, 1964.
(2) Steiner, J., Termonia, Y., and Deltour, J., “Comments on Smoothing
and Differentiation of Data by Simplified Least Squares Procedures,”
Analytical Chemistry, Vol 44, p. 1906, 1972.
(3) Willson, P. D. and Polo, S. R., “Polynomial Filters of Any Degree,”
Journal of the Optical Society of America, Vol 71, 1981, pp. 599–603.
(4) Blackburn, J. A., Analytical Chemistry, Vol 37, 1965, p. 1000.
(5) Antoon, M. K., Koenig, J. H., and Koenig, J. L., Applied
Spectroscopy, Vol 31, 1977, p. 578.

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