OVP PhEur 2.2.40

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OVP for

PhEur 2.2.40

User Manual

Version 7
© 2011 BRUKER OPTIK GmbH, Rudolf-Plank-Straße 27, D-76275 Ettlingen,
www.brukeroptics.com

All rights reserved. No part of this manual may be reproduced or transmitted in any
form or by any means including printing, photocopying, microfilm, electronic sys-
tems etc. without our prior written permission. Brand names, registered trademarks
etc. used in this manual, even if not explicitly marked as such, are not to be consid-
ered unprotected by trademarks law. They are the property of their respective own-
er.

This manual is the original documentation for the OPUS spectroscopic software.
Table of Contents

1 Introduction . . . . . . . . . . . . . . . . . . . . . . . 1
1 .1 Ph Eu r 2 .2 .4 0 T e s t s . . . . . . . . . . . . . . . . . . . . 1

2 Test Setup . . . . . . . . . . . . . . . . . . . . . . . . 3
2.1 Reference Standards . . . . . . . . . . . . . . . . . . . 4
2.2 Setting up OVP for PhEur 2. 2 . 4 0 . . . . . . . . . . . 6
2.3 Measure Laser Wavenumber . . . . . . . . . . . . . . 9
2 .4 OVP Te sts . . . . . . . . . . . . . . . . . . . . . . . . . 11
2.5 Reflection Measurement Mode . . . . . . . . . . . 13
2.6 Transmission Measurement Mod e . . . . . . . . . 22

3 Run OVP Tests . . . . . . . . . . . . . . . . . . . . 31


3 .1 Test sta tus . . . . . . . . . . . . . . . . . . . . . . . . . 32
3.2 Wh i c h t e s t s w i l l b e p e r f o rm ed? . . . . . . . . . . . 32
3.3 App e n d i ng co mme n t to the test report . . . . . . 33
3.4 Printing test reports . . . . . . . . . . . . . . . . . . . 33
3.5 Photometric Linearity Test . . . . . . . . . . . . . . 34
3.6 Ph o t o me t r i c N o i s e T e s t . . . . . . . . . . . . . . . . 35
3.7 Wavelength Uncertainty/Re producibility Te st . 36

4 Appendix - Wavelength Uncertainty Test


using Water Vapor . . . . . . . . . . . . . . . . . 39
4.1 Re f e re n c e s . . . . . . . . . . . . . . . . . . . . . . . . . 39
4.2 Document History . . . . . . . . . . . . . . . . . . . . 40
4.3 In tro d u cti on . . . . . . . . . . . . . . . . . . . . . . . . 40
4 .4 Purpose . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
4 .5 USP Re quireme nts . . . . . . . . . . . . . . . . . . . 41
4.6 Spectra Comparison of S RM 2035 and Wat er
V ap o r . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
4.7 Reference for Water Vapo r Absorbance . . . . . 46
4.8 Connes’ Advantage of Fourier Transform
Interferometry . . . . . . . . . . . . . . . . . . . . . . . 48
4.9 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . 49

Bruker Optik GmbH OVP for PhEur 2.2.40 iii


Table of Contents

iv OVP for PhEur 2.2.40 Bruker Optik GmbH


1 Introduction
This manual describes the OPUS Validation Program (OVP) for
spectrometer qualification according to the guidelines set forth by
the European Pharmacopoeia (PhEur). OVP for PhEur 2.2.40 is
part of the OPUS spectroscopic software. An additional registration
of the OPUS/PhEur 2.2.40 package is required.

The tests and test criteria intend to check the Bruker line of NIR
spectrometers and modules according to the PhEur regulations.
They are designed to follow the guidelines outlined in section
2.2.40 Near-Infrared Spectrophotometry by the European Pharma-
copoeia.

The PhEur 2.2.40 test protocol is to be performed in the context of


an OQ test. The OQ (Operational Qualification) test protocol
checks the instrument performance and compares this perfor-
mance to the instrument specifications. OQ tests should normally
run after installation, maintenance or major repair, exchange of
optical components which may influence the instrument perfor-
mance, on a regular yearly or semi-yearly basis.

1 .1 P h E u r 2. 2.4 0 Tes ts

• Photometric Linearity
• Photometric Noise (high light flux and low light flux)
• Wavelength Uncertainty
• Wavelength Reproducibility

For additional information on the different testing methods, refer to


European Pharmacopoeia, section 2.2.40.

For further general information on OVP refer to the OPUS Refer-


ence Manual.

Bruker Optik GmbH OVP for PhEur 2.2.40 1


Chapt. 1 Introduction

2 OVP for PhEur 2.2.40 Bruker Optik GmbH


2 Test Setup
OVP PhEur 2.2.40 supports reflectance channels as well as trans-
mittance channels. Depending on the specified measurement
channel OVP PhEur 2.2.40 detects the proper configuration auto-
matically.

If you select a reflectance channel, only the tests for reflectance


measurements will be activated.

If you select a transmission channel, only the test for the transmis-
sion measurement will be activated. In case of fiber optic pobes
you can select between reflectance (e.g. powder immersion probe)
and transmission mode (liquid probe).

Note: Once selected, the mode cannot be changed later.

Depending on the spectrometer type and test mode additional


external reference standards may be required. The following table
shows instrument types, test modes and standards which are used
for the different tests.

Note: Before setting up the tests make sure that the


required standards are available.

Bruker Optik GmbH OVP for PhEur 2.2.40 3


Chapt. 2 Test Setup

2.1 R eferen ce Stan dards

Photometric Linearity Test:

Instrument Type Test Mode Internal Standard External Standard

MPA Reflection None Gold Standard (for


MATRIX straylight correction
VECTOR 22/N spectra only)
Labsphere Standard
Set with 99% (Refer-
ence), 80%, 40%,
20%, 10%
optional: 5%

MPA with BRM 2065 Transmission Filter NG4 None


and Glass filters Filter NG9
NG4, NG9 and NG11 Filter NG11

MPA, MATRIX, VEC- Transmission Filter NG4 Filter NG11


TOR 22/N with Poly- Filter NG9
styrene and Glass
filter NG4 and NG9

High Flux and Low Flux Noise Test:

Instrument Type Test Mode Internal Standard External Standard

MPA Reflection None Labsphere Standards


MATRIX 99% and 10%
VECTOR 22/N

MPA with BRM 2065 Transmission Filter NG9 None


and Glass filters
NG4, NG9 and NG11

MPA, MATRIX, VEC- Transmission Filter NG9 None


TOR 22/N with Poly-
styrene and Glass
filter NG4 and NG9

4 OVP for PhEur 2.2.40 Bruker Optik GmbH


Reference Standards Chapt. 2

Wavelength Uncertainty and Wavelength Reproducibility Test:

Note: This test requires only a single standard - if standards


are listed in both the internal and external standard
column, you can either use the internal or external
standard.

Alternatively, you can use water vapor instead of ref-


erence standards for both reflection and transmission
mode. Details are given in attachment.

Instrument Type Test Mode Internal Standard External Standard

MPA Reflection None Gold Standard or Lab-


MATRIX sphere 99% for refer-
VECTOR 22/N ence measurement

SRM 1920a or
KTA 1920x or
SRM 2036 or
CH2Cl2 (Suspension
in TiO2)

MPA with BRM 2065 Transmission BRM 2065 SRM 2065 or


and Glass filters SRM 2035 or
NG4, NG9 and NG11 BRM 2065 or
CH2Cl2

All types of spectrom- Transmission and None None, measurement


eters reflection is based on reference
position of measuring
channel

MPA with BRM 2065 Transmission BRM 2065 Water vapor


and Glass filters
NG4, NG9 and NG11

MPA Reflection None Water vapor


MATRIX
VECTOR 22/N

Bruker Optik GmbH OVP for PhEur 2.2.40 5


Chapt. 2 Test Setup

2.2 Setting up OVP for PhEur


2.2.40

If you have already set up OVP for OQ (Operational Qualification)


and/or PQ (Performance Qualification), you can skip this chapter.

Before you can use OVP for PhEur 2.2.40 you have to set up the
corresponding PhEur 2.2.40 parameters and define the OVP test
channels and OVP tests.

1 On the Validation menu, select the OVP Setup command to


open the following dialog:

Figure 1: Setup OVP

2 Enter a title for the current configuration into the Title for new
configuration entry field, to specify the current setup by a
descriptive text.
3 Click the Add new configuration button. Now, all the other
selection fields will no longer be hidden and can be filled in.
4 Define the parameters for the test channel configuration.
5 Measure the laser wavenumber (see chapter 2.3).

6 OVP for PhEur 2.2.40 Bruker Optik GmbH


Setting up OVP for PhEur 2.2.40 Chapt. 2

6 Select the OVP tests (see chapter 2.4).


7 Store the test channel configuration.

Te s t c h a n n e l c o n f i g u r a t i o n

A
H

B I

D
J
E
F K
L
G

Figure 2: Setup OVP - Activated drop-down lists

A The drop-down list shows the test channel used by OVP.


B For each spectrometer test channel you have to assign a
measurement configuration to be used during actual valida-
tion measurement. This is a valid combination of source,
beam splitter, measurement channel and detector.
The respective entry is pre-defined in the appropriate selec-
tion field by default. As soon as you have selected the correct
entry the appropriate instrument configuration (D) and the bit-
map (H) specified for the measurement channel selected will
be proposed.
C To set up the laser wavenumber, click this button. See also
chapter 2.3.
D In general, the instrument configuration is displayed as soon
as you have selected all components. Always check whether
the correct instrument configuration has been suggested. If
required, select a different instrument configuration.
E Depending on the test channel (A), the drop-down list con-
tains appropriate accessories.

Bruker Optik GmbH OVP for PhEur 2.2.40 7


Chapt. 2 Test Setup

F Depending on the test channel and ATR accessory selected


the drop-down list contains appropriate crystal types. This
only applies to accessories with a changeable ATR crystal.
G For each type of accessory you can define a unique set of
measurement parameters, defined in a so-called measure-
ment experiment file. This file has the extension *.XPM.
Depending on the accessory defined you can select an
appropriate measurement experiment file from the drop-down
list.
H Depending on the measurement channel selected a configu-
ration-specific bitmap will be displayed.
I Use this button to load further instrument images available in
OPUS. The bitmaps are stored in the OPUS\VALIDA-
TION\Bitmaps directory. Note: Click the button and
select the Thumbnail option from the pop-up menu to be
able to see at once which bitmap belongs to which file
name. For details on the bitmaps refer to the OPUS Refer-
ence Manual, chapter 13.
J To delete the current configuration click this button. Once
deleted the settings cannot be reloaded. Note: If you have
accidentally deleted a channel, you have to repeat the
complete setup again. OVP configurations are stored in
the OPUS\VALIDATION\Database\<Instrument><Serial
Number> (e.g. MPA_042_03) directory.
K This button allows to reset the accessory type selection. This
is only required if you have selected a wrong type of acces-
sory and used this type to perform a wavenumber calibration.
L In special situations, this field contains information on the set-
up of test channels.

8 OVP for PhEur 2.2.40 Bruker Optik GmbH


Measure Laser Wavenumber Chapt. 2

2.3 Measure Laser Wavenum-


ber

Before starting the instrument test for the current configuration you
may first have to calibrate the laser wavenumber (LWN). Measur-
ing and assigning the laser wavenumber for the current test chan-
nel ensures the wavenumber accuracy of spectral data.

Note: For detailed information on the LWN calibration refer


to the OPUS Reference Manual, chapter 13.

To c a l i b r a t e t h e l a s e r w a v e n u m b e r.. .

1 ...make sure that the correct test channel has been selected.

2 Click the button in the Setup OVP dialog (see


figure 2).

When calibrating...

...a water vapor spectrum is measured. Then, the optimum laser


wavenumber is determined on the basis of a specific water band.
To verify the validity of this water band adjacent water bands are
checked as well.

In a second step the appropriate wavenumber is verified on the


basis of the bands of the filter material on the internal validation
unit.

A ft e r c a l i b r a t i o n . . .

1 ...a result dialog pops up.

Bruker Optik GmbH OVP for PhEur 2.2.40 9


Chapt. 2 Test Setup

Figure 3a: LWN calibration okay 7b: Set LWN

If the LWN has to be set (see figure 3b), click the YES but-
ton.

Note: For detailed information on how to interpret the LWN


calibration result refer to the OPUS Reference Man-
ual, chapter 13.

2 ...a green check mark is added to the button in


the Setup OVP dialog.

Figure 4: Setup OVP dialog after LWN calibration

10 OVP for PhEur 2.2.40 Bruker Optik GmbH


OVP Tests Chapt. 2

2.4 O VP Tests

If you click the OVP Test Setup tab, the following dialog opens:

Figure 5: OVP Test Setup tab

1 The test interval period is defined by default for the two test
categories. If you want to change the interval, type the
interval period into the entry field and select the units from
the drop-down list. Available units are hours, days, or
months.
2 Activate the Run check box.
3 Select PhEur 2.2.40 from the first drop-down list and the OQ
test category from the second.

Bruker Optik GmbH OVP for PhEur 2.2.40 11


Chapt. 2 Test Setup

Figure 6: Configuring PhEur 2.2.40 test

4 Click the Setup button to open the PhEur 2.2.40 Test Proto-
col dialog (see chapter 2.5).
5 If all tests have been set up and you click the OK button, the
setup status is indicated by a green check mark.

12 OVP for PhEur 2.2.40 Bruker Optik GmbH


Reflection Measurement Mode Chapt. 2

2.5 R eflection Measurement


Mode

Figure 7: PhEur 2.2.40 Test Protocol - TestSetup for reflection

First, define the correct type of measurement, i.e. either reflection


or transmission. Activate the corresponding option button.

Figure 7 shows the setup dialog for reflection measurement. Ini-


tially, all tests are selected in the Test Selection group field. In case
of a configuration with an integrating sphere the standard OQ/PQ
tests for OVP normally use the internal reference position (e.g.
Sphere Background for the MPA). For PhEur tests, however, exter-
nal standards have to be measured. Therefore, the Measurement
Channel drop down list allows to select the channel used for these
measurements.

Bruker Optik GmbH OVP for PhEur 2.2.40 13


Chapt. 2 Test Setup

To perform all four tests make sure that all test options are
selected. There is a separate page for each test selected. Note that
at least one test has to be selected.

2.5.1 P h o t o m e t r i c L i n e a r i t y Te s t

The photometric linearity test is performed using a set of reflec-


tance standards of known relative reflectance (Labsphere Stan-
dard).

According to PhEur 2.2.40 the spectra obtained from reflectance


standards are subject to variability due to the difference between
the experiment conditions under which they are factory-calibrated
and those under which they are subsequently used.

Hence, the percent reflectance values supplied with the calibration


certificate may not be useful to establish an absolute calibration for
a given instrument. However, as long as the standards have the
same physical description, the same reference background is
used, and the target instrument measures each under identical set-
tings, the reproducibility of the photometric scale will be established
over the range of standards used. Subsequent measurements give
information on long-term stability.

The photometric linearity test requires a set of certified reflectance


standards with known reflectance values. PhEur 2.2.40 requires
one standard (99%) for reference and at least four standards for
the test itself (80%, 40%, 20% and 10%). When measuring sam-
ples of low reflectance an additional low reflecting standard (5%) is
required.

Before you can start the test, you have to read-in the data for the
certification table. These data are provided in digital form on a CD.
If you have your own standard set, you can read-in and store these
data. If you want to use leased standards, we recommend to only
enter the path to the CD drive or memory stick only. As soon as the
test runs, these data will be read by the respective medium.

14 OVP for PhEur 2.2.40 Bruker Optik GmbH


Reflection Measurement Mode Chapt. 2

Click the Photometric Linearity tab to open the following dialog:

B
E
C

H
F

Figure 8: PhEur 2.2.40 Test Protocol - Photometric Linearity tab

A If you click this button, a load dialog opens. Load the text file
with the certificate values. The text file is normally delivered
with the set, provided the set was purchased from Bruker.
Table G and the drop-down lists C and D correlate to the data
of the standard file.
B The report number identify the set of standards. The report
number is also listed in the certificate.
C The date of calibration is also read and listed in the certificate.
D If you activate this check box, the file with the standard data is
read when the test runs.
E Here you can enter the path of the file with the standard data.
If you do not enter the path, you will be prompted to do so
when the test runs. Alternatively, click the to select the path.
F Select the number of standards to be measured for the test
(excluding the 99% reference standard).

Bruker Optik GmbH OVP for PhEur 2.2.40 15


Chapt. 2 Test Setup

G Depending on the number of standards selected, the table


shows only those columns which are used for the test.
H The test uses the average reflectivity of 5 frequencies.
I Activate this check box if a stray light correction has to be
done prior to the evaluation of test spectra. If you measure by
using an integrating sphere it is essential to use the stray light
correction for this test. For details about the stray light correc-
tion and how to record the correction spectra refer to the
OPUS Reference Manual.

S o m e h i n ts f o r d a ta e n t r y

If the file with the standard data has not been supplied, you have
to generate such a file. For details see chapter 4.

Figure 9: Text file example for data input

16 OVP for PhEur 2.2.40 Bruker Optik GmbH


Reflection Measurement Mode Chapt. 2

• You do not need to add factors for every column of


reflection standard, only enter the data for standards you
will be using.
• You have to enter a value for every frequency in the
table.

2.5.2 P h o t o m e t r i c N o i s e Te s t

The photometric noise test involves measuring spectra of high and


low light throughput which is achieved by using high and low reflec-
tance material. The analysis is performed by measuring the peak-
to-peak noise level in successive 100nm (300cm-1) spectral seg-
ments, between 1200 and 2200nm (8300 and 4500cm-1). Depend-
ing on the measurement channel a different frequency range may
be used.

The High Light Flux measurement uses the LabsphereTM 99%


(SRS-99-010) standard.

The Low Light Flux measurement uses the LabsphereTM 10%


(SRS-10-010) standard. This measures system performance at
reduced light level. Noise from the source, detector, optics, and
electronics make significant contributions at this level.

Bruker Optik GmbH OVP for PhEur 2.2.40 17


Chapt. 2 Test Setup

Figure 10: PhEur 2.2.40 Test Protocol - Photometric Noise tab

A Activate this check box if you want to perform the High Flux
Noise measurement.
B Activate this check box if you want to select the Low Flux
Noise measurement.
C The measurement range used for the specified channel. The
range is recommended by PhEur 2.2.40 but may be different
if the instrument does not support this range.

2.5.3 Wa v e l e n g t h U n c e r ta i n t y Te s t

This test provides information on the long-term stability of the spec-


trometer wavelength uncertainty. In case of the wavelength uncer-
tainty test you can choose between two test methods.

The recommended method measures a specific peak of water


vapor. This has the advantage of not requiring a reflectance stan-
dard, and the position of the water vapor band can be checked

18 OVP for PhEur 2.2.40 Bruker Optik GmbH


Reflection Measurement Mode Chapt. 2

much more precisely. The appendix describes the advantages of


using water vapor for this test.

Figure 11: PhEur 2.2.40 Test Protocol - Wavelength Uncertainty test

A Activating the Use Water Vapor option button measures a


water vapor peak using the standard peak-picking algorithm.
B According to PhEur 2.2.40 two water bands are suited for this
test. Select either the band at 7306.736cm-1 (recommended)
or the band at 7299.449cm-1.

The alternative method requires the use of a certified reference


standard like NIST 1920a, NIST SRM 2065, KTA 1920x or CH2Cl2
(TiO2 suspension). A standard background measurement is per-
formed, and then the standard is measured. The specific peaks for
the reflectance standards are measured with their values deter-
mined using the center of gravity algorithm.

The band positions are listed in the certificate provided with the ref-

Bruker Optik GmbH OVP for PhEur 2.2.40 19


Chapt. 2 Test Setup

erence standard. Some certificates list frequencies for a different


resolution. Make sure that you choose the frequency values from
the column with the specified resolution of 4cm-1.

Figure 12: PhEur 2.2.40 Test Protocol - Wavelength Uncertainty test

A Select the standard to be used for the test. When using water
vapor B to E will not be visible.
B Select the standard to be used from the drop-down list.
C This line shows the recommended frequencies to be used for
evaluation. Select bands from the certificate which are in
close vicinity to these frequencies.
D Enter the band positions as provided in the certificate into the
three entry fields.
E Depending on the standard the frequencies in the certificate
can be listed in nanometers or wavenumbers. Thus, the val-
ues can either be entered in nanometers or as wavenumbers.
Select the required units by activating the respective option
button.

20 OVP for PhEur 2.2.40 Bruker Optik GmbH


Reflection Measurement Mode Chapt. 2

2.5.4 Wa v e l e n g t h R e p r o d u c i b i l i t y Te s t

This test uses the parameters, settings and standards as specified


for the wavelength uncertainty test, except that only a single band
is used for evaluation.

Ten sample measurements are performed and the band location of


the specified band is evaluated for all ten spectra. Based on the
band location of these 10 single measurements the average is cal-
culated.

The maximum deviation is determined from this average. The devi-


ation must not exceed a specified limit, which depends on the type
of standard used. The table below shows the evaluated band and
maximum deviation of a few standards. Depending on the measur-
ing channel the values can also deviate.

Standard Band used (cm-1) Maximum Deviation (cm-1)

Water vapor 7306.736 0.05

NIST SRM 2036 10245 0.1

Ch2Cl2 6064 0.1

Bruker Optik GmbH OVP for PhEur 2.2.40 21


Chapt. 2 Test Setup

2.6 Transmission Measure-


ment Mode

Figure 13: PhEur 2.2.40 Test Protocol - TestSetup for transmission

The test setup for the transmission mode is very similar to the one
for reflection mode. Initially all tests are selected. The Test Selec-
tion group field contains all tests available for transmission mea-
surement.

To perform all four tests, select all the test options. There is a sep-
arate page for each test selected. Note that at least one test has to
be selected.

22 OVP for PhEur 2.2.40 Bruker Optik GmbH


Transmission Measurement Mode Chapt. 2

2.6.1 P h o t o m e t r i c L i n e a r i t y Te s t

The photometric linearity test is performed using the open channel


and three different glass filters which are mounted on the internal
validation unit (IVU) of your spectrometer. Currently no external
certified transmission standards with known transmission values
are available.

Similar to the reflectance measurements the evaluation uses three


different frequencies over the measurement range. The frequen-
cies have been selected with respect to the filter material which
does not provide a linear transmission over the full range. The fil-
ters have been selected such that an as large as possible range of
transmission values is covered.

According to PhEur 2.2.40 the measurements are not possible to


establish an absolute calibration for a given instrument. However,
as long as the standards have the same physical description, the
same reference background is used, and the target instrument
measures each under identical settings, the reproducibility of the
photometric scale will be established over the range of standards
used. Subsequent measurements give information on long-term
stability.

To set up a photometric linearity test you have to measure refer-


ence values before you can run the test. Reference measurements
should only be repeated after replacement of optical components
or major repair.

Note: In case of instruments without the internal NG11


glass filter you will be asked during the reference
measurement to insert the external NG11 standard
which is available at Bruker.

Bruker Optik GmbH OVP for PhEur 2.2.40 23


Chapt. 2 Test Setup

Figure 14: PhEur 2.2.40 Test Protocol - Photometric Linearity tab

A The Filter Setting column shows the filters used for testing.
The filters are determined by the program.
B The values for the reference measurement are displayed in
the table.
C Click this button to measure the reference spectra.
D These lines show if and when the last reference has been
measured. In the latter case the date and time of the mea-
surement is also displayed. These lines also show whether a
reference measurement is in progress.

The transmission values are retrieved from the spectra and filled in
the table. Typical filter spectra and the frequencies used for evalua-
tion are shown in figure 15.

24 OVP for PhEur 2.2.40 Bruker Optik GmbH


Transmission Measurement Mode Chapt. 2

Figure 15: Typical filter spectra

2.6.2 P h o t o m e t r i c N o i s e Te s t

The photometric noise test involves measuring spectra using the


Open Channel (High Flux) and one of the glass filters (Low Flux)
on the IVU (internal validation unit).

The filter used has as low transmissivity. The analysis is performed


by tabulating the Peak to Peak (PP) noise level in successive
100nm (300cm-1) spectral segments between 1200 and 2200nm
(8300 and 4500cm-1) and the average of these values. Depending
on the measurement channel a different frequency range may be
used.

The High Flux Noise measurement uses the open channel. The
Low Flux Noise measurement uses the glass filter NG9. This mea-

Bruker Optik GmbH OVP for PhEur 2.2.40 25


Chapt. 2 Test Setup

sures system performance at reduced light levels. Noise from the


source, detector, optics, and electronics make significant contribu-
tions at this level.

With some spectrometer configurations this high flux test cannot be


performed. In this case the test is deactivated.

Figure 16: PhEur 2.2.40 Test Protocol - Photometric Noise tab

A Activate this check box if you want to perform the High Flux
Noise measurement.
B Activate this check box if you want to perform the Low Flux
Noise measurement.
C The measurement range used for the specified channel. The
range is recommended by PhEur 2.2.40 but may be different
if the instrument channel does not support this range.

26 OVP for PhEur 2.2.40 Bruker Optik GmbH


Transmission Measurement Mode Chapt. 2

2.6.3 Wa v e l e n g t h U n c e r ta i n t y Te s t

This test provides information on the long-term stability of the spec-


trometer wavelength uncertainty. In case of the wavelength uncer-
tainty test you can choose between two test methods.

The method recommended by Bruker measures a specific peak of


water vapor. This has the advantage of not requiring a transmis-
sion standard and also grants a much higher precision. The appen-
dix describes the advantages of using water vapor for this test.

Figure 17: PhEur 2.2.40 Test Protocol - Wavelength Uncertainty test

A Activating the Use Water Vapor option button measures a


water vapor peak using the standard peak-picking algorithm.
B Two water bands are suited for this test. Select either the
band at 7306.736cm-1 (recommended) or the band at
7299.449cm-1.

Bruker Optik GmbH OVP for PhEur 2.2.40 27


Chapt. 2 Test Setup

External standards, like NIST SRM 2065, SRM 2035 or CH2Cl2


can be purchased and used as well. As internal standard Bruker
offers the BRM 2065 reference standard which is mounted on the
IVU (internal validation unit) and which allows to run all tests fully
automatically. A certificate is available for this standard.

Note: For instruments without the internal BRM 2065 an


external transmission standard (e.g. BRM 2065) is
required if you want to use a standard. This standard
is available from Bruker.

First, a background measurement is performed. Then, the standard


is measured. The specific frequency peaks for the reflectance stan-
dards are measured with their values determined using the center
of gravity algorithm.

The band frequencies are listed in the Certificate of Analysis pro-


vided with the reference standard. If the certificate contains values
for different spectral resolutions, make sure that you select the fre-
quency values from the column with the specified resolution of
4cm-1.

Recommended band frequencies vary for different standards and


are shown on the Wavelength Uncertainty page. Thus, before
entering the reference values from the certificate make sure the
proper reference standard has been selected from the standards
drop-down list.

28 OVP for PhEur 2.2.40 Bruker Optik GmbH


Transmission Measurement Mode Chapt. 2

Figure 18: PhEur 2.2.40 Test Protocol - Wavelength Uncertainty test

A Select the standard to be used for the test. When selecting


water vapor as reference standard B to E will not be visible.
B Select the standard to be used from the drop-down list.
C This line shows the recommended peaks to be used for eval-
uation. First, select the standard as described in A.
D Three entry fields are provided to enter the peak frequencies
as provided in the certificate. When using the internal stan-
dard with newer spectrometers, the data of the standard are
automatically read and entered. In this case you are not
allowed to enter or modify any data. Additionally, a tempera-
ture corerction of the band position is performed during the
test run.
E Depending on the standard the frequencies in the certificate
can be listed in nanometers or wavenumbers. The values can
thus either be entered in nanometers or as wavenumbers.
Select the required units by activating the respective option
button.

Bruker Optik GmbH OVP for PhEur 2.2.40 29


Chapt. 2 Test Setup

2.6.4 Wa v e l e n g t h R e p r o d u c i b i l i t y Te s t

This test uses the same parameters, settings and standards as


specified for the wavelength uncertainty test. If a reference stan-
dard is selected for the wavelength reproducibility test, the fre-
quency specified in the first entry field is used (D in figure 18).

A reference measurement is only required if the wavelength uncer-


tainty test had not been run before. Ten sample measurements are
performed and the band location of the specified band is evaluated
for all ten spectra.

Based on the band location of these 10 single measurements the


average is calculated. The maximum deviation determined from
this average. The deviation must not exceed a specified limit,
which depends on the type of standard used.

The table below shows the evaluated band and maximum deviation
of a few standards.

Standard Band used (cm-1) Maximum Deviation (cm-1)

Water vapor 7306.736 0.05

NIST SRM 2036 10245 0.1

Ch2Cl2 6064 0.1

30 OVP for PhEur 2.2.40 Bruker Optik GmbH


3 R u n O V P Te s ts
There are two possibilities to run OVP tests. Either by selecting the
Run OVP Tests command on the Validation menu or by clicking the

status light ( ) and using the Instrument Status dialog. For


details on the letter case refer to the OPUS Reference Manual,
chapter 13.

1 On the Validation menu, click the Run OVP Tests command.


The following dialog opens:

Figure 19: Run OVP Tests

2 Select the test channel and test category.


3 Click the Run selected Tests button.

Bruker Optik GmbH OVP for PhEur 2.2.40 31


Chapt. 3 Run OVP Tests

3 .1 Test stat us

The line below the test channel shows the tests set up for this
channel, and their status.

Figure 20: OVP test status

Test status What happens?

Test has expired. Test is activated.

Test has not expired yet. Test is not activated. The remaining
time is indicated as reminder.

Test has not yet been performed. Test is activated.

If a test has not expired, but the interval has only e.g. 2 hours left
you can activate the check box for that test and run the test earlier.

If a test has expired, but you are not prepared to perform that test
(external standards required), you can deactivate the check box for
the corresponding test.

3.2 Which tests will be per-


formed?

As soon as you have activated the check box for the respective test
protocol you can see which test(s) will be performed by the
browser-like display below the bitmap.

32 OVP for PhEur 2.2.40 Bruker Optik GmbH


Appending comment to the test report Chapt. 3

3.3 A ppending comment to the


test report

The test results are stored in a report (PDF file).

To append a comment to the current test protocol entry write a


comment into the User Comment entry field (figure 19).

3.4 Printing test reports

The test results are stored and recorded as a report in PDF format
in the UserData database.

The test report contains a summarized test result page and addi-
tional pages with all the test spectra for each test.

Reports are stored in the separate VALIDATION\REPORTS direc-


tory and can be displayed and/or printed.

Note: To have the report displayed and printed you require


the Adobe Acrobat Reader which is available on the
OPUS installation stick.

Bruker Optik GmbH OVP for PhEur 2.2.40 33


Chapt. 3 Run OVP Tests

3.5 Photometric Linearity Te st

3.5.1 Reflection Measurement

Prerequisites:
• The photometric linearity test for reflection measure-
ments requires the use of the 99% reflectance stan-
dard (SRS-99-010) for reference (background)
measurement.
• For an integrating sphere the straylight correction
spectra must have been measured using a Bruker certi-
fied gold standard and a light trap (if available). The cer-
tified reflection factor of the gold standard and light trap
has to be defined to measure the straylight correction
spectrum.
• For an integrating sphere the straylight correction
check box in the PhEur setup has to be set and the
proper measuring channel selected.
• For an integrating sphere an 8 degree sample holder
for Labsphere Standards has to be used.
• For a fiber solid probe the straylight correction must not
be used. Instead, use an appropriate sample holder.

Follow the wizard instructions and position the standard, depend-


ing on the method used with your spectrometer configuration.

Note: The measurement requires specialized holders for the


reference standards.

After the background measurement has completed, you will be


prompted for each of the reflectance standards selected in the
PhEur Setup dialog. Insert the respective standard into the sample
holder, and follow the instructions to perform the measurements. If
each of the standards has been measured, the final results will be
computed.

34 OVP for PhEur 2.2.40 Bruker Optik GmbH


Photometric Noise Test Chapt. 3

3.5.2 Tr a n s m i s s i o n M e a s u r e m e n t

Prerequisites:

The Photometric Linearity test for transmission measurements


uses the glass filters mounted on the IVU (Internal Validation Unit).
The test itself runs fully automatically and needs no user interac-
tion.
• For instruments with only two glass filters on the IVU an
external NG 11 glass filter is required. You will be
prompted to insert the glass filter into the sample posi-
tion.

3.6 Photometric Noise Test

3.6.1 Reflection Measurement

Prerequisites:
• The Photometric High Light Flux Noise test for reflection
measurements requires the Labsphere 99% reflec-
tance standard (SRS-99-010).
• The Photometric Low Light Flux Noise test for reflec-
tance measurements requires the Labsphere 10%
reflectance standard (SRS-10-010).
• For an integrating sphere an 8 degree sample holder
for Labsphere Standards must be used.

Follow the wizard instructions and insert the standard into the sam-
ple holder, depending on the method used with your instrument
configuration. You will be prompted for each of the standards.

Note: The measurement requires specialized holders for the


reference standards.

For each test (High or Low Light Flux) a background and sample
measurement are made using the reflectance standard. At the end
of the test the final results are computed.

Bruker Optik GmbH OVP for PhEur 2.2.40 35


Chapt. 3 Run OVP Tests

3.6.2 Tr a n s m i s s i o n M e a s u r e m e n t

Prerequisites:
• None

The photometric noise test for transmission measurements is per-


formed by using the Open Channel (High Light Flux) and a filter on
the IVU (Low Light Flux). The test itself runs fully automatically and
needs no user interaction.

3.7 Wavelength Uncertainty/


Rep ro d u cib ility Te s t

3.7.1 Reflection Measurement

Prerequisites:
• The wavelength uncertainty and wavelength reproduc-
ibility test for reflection measurements require the use of
either the 99% reflectance standard (SRS-99-010) or a
gold standard for the background measurement.
• Unless water vapor is used for these tests an external
certified reference standard (see table in chapter 2.1)
is required for the sample measurement.

The background measurement for these tests can be performed


using the standard method used for your spectrometer and config-
uration (e.g. gold standard for integrating sphere, reference posi-
tion for fiber optics solid probe etc.) Instead of the gold standard,
the 99% Labsphere Reference standard can be used. Both tests
use the same background measurement.

36 OVP for PhEur 2.2.40 Bruker Optik GmbH


Wavelength Uncertainty/Reproducibility Chapt. 3

Follow the wizard instructions and position the standard on the


sample holder, depending on the method used with your instru-
ment configuration.

Note: This may require specialized holders for the reference


standard.

At the end of the test the final results will be computed.

3.7.2 Tr a n s m i s s i o n M e a s u r e m e n t

Prerequisites:
• In case of transmission measurements the reference
(background) measurement for the wavelength uncer-
tainty test is run with the open channel.
• Unless water vapor is used for this test either an exter-
nal certified reference standard (see table in
chapter 2.1) or the internal reference standard (BRM
2065) on the IVU with certificate is required for the sam-
ple measurement.

You will be prompted for the standard to be inserted only if an


external reference standard has been selected.

Note: Special sample holders may be required when mea-


suring external standards. If the internal BRM 2065
standard or water vapor has been selected, the test
will run without any further user interaction.

Bruker Optik GmbH OVP for PhEur 2.2.40 37


Chapt. 3 Run OVP Tests

38 OVP for PhEur 2.2.40 Bruker Optik GmbH


4 A p p e n d i x - Wa v e -
l e n g t h U n c e r ta i n t y
Te s t u s i n g Wa t e r
Va p o r
4.1 R eferen ces

[1]Second Supplement, USP-NF <1119> Near-Infrared Spectro-


photometry

[2]H2O vapor calibration-engl.doc, Dr. Axel Keens, 31 May 2001

[3]2035.pdf, National Institute of Standards & Technology, Certifi-


cate, Standard Reference Material® 2035

[4]C. Kradjel, U. Grummisch, R. Rachlis, in: "Making Light Work:


Advantages in Near Infrared Spectroscopy", Developed from the
4th International Conference on Near Infrared Spectroscopy, Aber-
deen, Scotland, August 19-23, 1991; edited by I. Murray and I.A.
Cowe, VCH Weinheim, 1992, Page 470.

[5]H. Günzler, H.M. Heise, "IR-Spektroskopie, Eine Einführung"; 3.


Auflage, VCH Weinheim, 1996, Seite 84.

[6]J. Gronholz, W. Herres, "Understanding FT-IR Data Process-


ing", I&C, Dr. Alfred Huethig Publishers, 1984, Page 2.

[7]H. Gremlich, Infrared and Raman Spectroscopy (§2.1),Ullmann's


Encyclopedia of Industrial Chemistry, 1994, VCH.

[8]P. Griffiths, Fourier Transform Infrared Spectrometry (§1 VII),


1986, Wiley, ISBN 0-471-09902-3
Bruker Optik GmbH OVP for PhEur 2.2.40 39
Chapt. 4 Appendix - Wavelength Uncertainty Test us-

4.2 D ocument History

ISSUE DATE AUTHOR Description File name

REVISION 1 10/09/2002 Andrea Giehl Wavelength uncer- Wavelength


tainty test for Bruker accuracy.doc
FT-NIR spectrometer

4.3 I ntroduction

Wavelength uncertainty test is part of the instrumental tests


needed for the qualification of an NIR spectrometer in accordance
with:
• USP Pharmacopoeia Forum <1119> 26(2000) 237-247
• Ph. Eur. III, 2.2.40 Near-Infrared Spectrometry, 43-44

This test is to ensure that the measured wavelengths are accurate


and remain accurate for measurements in diffuse reflectance or
transmittance mode.

4.4 Purpose

The purpose of this document is to provide detailed information on


the use of water vapor absorbance bands for the calibration and
validation of Fourier Transform NIR spectrometers. Measuring the
water vapor absorbance band at a single wavenumber shall
replace the wavelength uncertainty test of Michelson- type FT-NIR
spectrometers required by USP, for both diffuse reflection and
transmission measurements.

Note: wavenumber = 1/wavelength

40 OVP for PhEur 2.2.40 Bruker Optik GmbH


USP Requirements Chapt. 4

4.5 U SP Requirements

In [1] the regulations are set for the Instrument Operational Qualifi-
cation with regards to Wavelength Uncertainty. They are as fol-
lows:

Wavelength Uncertainty: [Note: The method used in developing


wavelength uncertainty values is based on the NIST Center of
Gravity algorithm.] Potential problems with internal calibration
schemes are avoided by specifying appropriate independent exter-
nal wavelength standards. For the reflectance mode, the NIST
SRM 1920a reflectance standard is preferred. Standards contain-
ing dysprosium or holmium oxide are available. The nature and
type of background reference standard must also be specified. In
transmittance measurements, the corresponding rare earth solu-
tion1 or glass standards can be used. Solid or sealed solutions can
be maintained similarly to a set of calibration weights to provide
information on long term stability2.
Table 0: Recommended Near-Infrared Instrument specificationsa

1. Holmium oxide solution, NIST SRM 2034, (wavelength standard from 240 to
650nm) may be used currently in the 650 to 1100nm region, although bands are
not certified in this region.
2. A rare earth oxide in glass transmission wavelength standard, SRM 2035, has
been certified recently by NIST. This standard may be used in transflectance
mode, but is not currently certified for such use.

Bruker Optik GmbH OVP for PhEur 2.2.40 41


Chapt. 4 Appendix - Wavelength Uncertainty Test us-

SRM 1920a peaksb occur at 1261, 1681 and 1935nm

Wavelength
Uncertainty

Tolerances 1nm at 1200nm or 8cm-1 at 8300cm-1


1nm at 1600nm or 4cm-1 at 6250cm-1
1.5nm at 2000nm or 4cm-1 at 5000cm-1

a A maximum nominal instrument resolution of 10nm at 2500nm or 16cm-1 at


4000cm-1 is appropriate for most applications.
b The nominal 1935nm peak depends on the instrument resolution. Use the
wavelength value from the SRM 1920a certificate, which comes close to the res-
olution used.

4.6 Spectra Comparison of


SRM 2035 and Water Va por

The NIST SRM 2035 transmittance standard is recommended by


USP to be used to determine the wavelength accuracy for trans-
mission measurements. Using the Center of Gravity (COG) of the
absorbance peaks (instead of the peak maximum), the instrument
can be considered as being qualified in the region from 10300cm-1
(971nm) to 5130cm-1 (1949nm). Spectra of this standard are
shown in figure 21 and figure 22 (in wavenumbers).

For the NIST SRM 2035 transmittance standard, the maximum


allowed deviations specified in the certificate depend on the investi-
gated absorbance band and the applied resolution. The NIST cer-
tificate [3] applies to the COG of 7 wavelength bands (certified in
nm and cm-1).

Examples for an FT instrument with a resolution of 4cm-1:

5138.45cm-1, 6804.65cm-1, 7313.46cm-1, 8178.58cm-1, 8681.56cm-1,


9293.38cm-1, 10245.43cm-1

The NIST certificate provides the uncertainty on the measurements


which are said to be about equivalent to a 95% confidence interval.
The actual limits for the allowed deviations are, however, not
42 OVP for PhEur 2.2.40 Bruker Optik GmbH
Spectra Comparison of SRM 2035 and Water Chapt. 4

defined in the certificate or the USP guideline. When determining


the band position the same center of algorithm (COG) has to be
used as the algorithm applied by NIST.

Figure 21: SRM 2035 spectrum, transmission wavelength standard, mixture of


rare earth oxides

Bruker Optik GmbH OVP for PhEur 2.2.40 43


Chapt. 4 Appendix - Wavelength Uncertainty Test us-

resolution: 2cm-1
resolution: 16cm-1

Figure 22: The sharpest absorption band in the SRM 2035 spectrum

SRM 2035

Water vapor

Figure 23: Comparing SRM 2035 and water vapor at a resolution of 2cm-1

44 OVP for PhEur 2.2.40 Bruker Optik GmbH


Spectra Comparison of SRM 2035 and Water Chapt. 4

The measurement of water vapor can be used to check the wave-


length accuracy for Michelson-type FT instruments. The water
vapor absorbance peak at e.g. 7306.74cm-1 measured with a high
resolution can be applied. Water vapor has the advantage of hav-
ing an extremely narrow band, and the wavelength position can be
measured to a very high degree of accuracy. This gives a more
precise measurement of the wavelength accuracy than would be in
case of NIST SRM 2035 standard (see figure 23). The NIST SRM
2035 standard itself is calibrated against the water vapor band (see
[3]).

In addition, using only one point (e.g. 7306.74cm-1 for water vapor)
to determine the wavelength accuracy test is sufficient for a Michel-
son-type FT instrument. The wavelength in an FT- instrument is
calibrated by an internal He/Ne laser with a wavelength of 633nm.
The value of the He/Ne wavenumber is entered in the control soft-
ware of the instrument and slightly adjusted so that this specific
water line is accurately registered in wavenumber - and hence
wavelength - by taking the reciprocal.

Theoretically, for an FT instrument, all wavelengths across the


entire spectrum will be accurately determined from this single set-
ting. Repeated measurements of the water vapor line with a cali-
brated FT instrument will show residual fluctuations due to
spectrometer noise. These shifts, however, are extremely small
and can be neglected. The residual fluctuations at all other wave-
lengths will be of a similar negligible amount.

Bruker Optik GmbH OVP for PhEur 2.2.40 45


Chapt. 4 Appendix - Wavelength Uncertainty Test us-

4.7 R eferen ce for Wa ter Va por


Absorban ce

Figure 24: Spectrometer calibration using the water vapor band at 7,306.74cm-1

There is no certification needed for water vapor as it represents a


natural constant and is always the same substance present in the
ambient air. It can be used for both transmittance and diffuse
reflectance measurements. Details on the reference values of the
water vapor absorbance peaks are given below [2]:

Ref.: Reference values for the calibration of Bruker FT-NIR spec-


trometers with reference to the water band at 7,306.74cm-1

The data is obtained (data source is) from the HITRAN 1992 data-
base, published by:

Air Force Phillips Laboratory


29 Randolph Road
Hanscom AFB, MA, 01731-3010

Dr. Laurence Rothman, PL/GPOS

46 OVP for PhEur 2.2.40 Bruker Optik GmbH


Reference for Water Vapor Absorbance Chapt. 4

M I wn[cm-1] S E“ v“ v’ Q’ Q“

H2O 1 7299.44900 1.300E-20 42.372 000 101 211 110

H2O 1 7303.23140 6.889E-22 95.176 000 200 322 211

H2O 1 7305.08049 3.149E-22 326.625 000 200 606 515

H2O 1 7306.73600 2.000E-20 79.496 000 101 313 212

H2O 1 7306.74700 1.000E-21 325.348 000 200 616 505

H2O 1 7308.81782 6.179E-22 136.762 000 101 322 303

H2O 1 7310.34759 1.949E-22 326.625 000 101 514 515

H2O 1 7310.67785 5.959E-21 134.902 000 101 322 221

H2O 1 7312.27100 7.400E-21 70.091 000 101 303 202

M: Molecule
I: Isotope; 1= 1H 16O 1H
wn: Vacuum wavenumber [cm-1]
S: Intensity [cm-1/(Molecule · cm-2) at 296K]
E“: Energy of the lower state [cm-1]
v“: Global Quantum numbers of the lower state
v’: Global Quantum numbers of the upper state
Q’: Local Quantum numbers of the upper state
Q“: Local Quantum numbers of the lower state

The reference band is the one with the largest intensity S (row 4).
The wavenumber is usually regarded as a constant as it is inde-
pendent of the refractive index of the surrounding medium.

A Fourier Transform Spectrometer (FTS), however, measures


wavelengths and thus depends on the refractive index of the
medium. The wavenumber (=1/  ) is calculated from the wave-
length by FFT (Fast Fourier Transformation).

As the refractive index of the air is subject to a dispersion (at


15800cm-1 it is higher than at 7300cm-1), the wavenumber range
becomes distorted in a non-linear way (the effect, however, is
extremely small). Therefore, it is possible to exactly calibrate an

Bruker Optik GmbH OVP for PhEur 2.2.40 47


Chapt. 4 Appendix - Wavelength Uncertainty Test us-

FTS under standard pressure only over a small range. The spectra
which are calibrated in this way are indicated in vacuum wavenum-
bers.

When converting vacuum wavenumbers into wavelengths, you


have to divide by the refractive index of the air. This index amounts
to 1.0002735 for dry standard atmosphere at 7300cm-1.

4.8 C onnes’ Advanta ge of Fou-


rier Transform Interferome-
try

The fact that only one point (e.g. 7306.74cm-1 for water vapor) is
required for the wavelength accuracy test is due to the Connes'
advantage of the Fourier Transform Infrared technique (see [4] to
[8]).

"In an FT spectrum, the accuracy of each wavenumber is coupled


to the accuracy with which the position of the moving mirror is
determined; by using an additional HeNe laser interferometer the
position of the mirror can be determined to an accuracy better than
0.005nm. This means that the wavenumbers of an FT-NIR spec-
trum can be determined with high accuracy (<0.01cm-1). In other
words, FT-IR spectrometers have a built-in wavenumber calibration
of high precision. This advantage is known as Connes' advantage"
(see [7]).

Due to the Connes' advantage there is no distortion of the fre-


quency in the spectrum and the x-axis may be calibrated exactly by
a single frequency.

48 OVP for PhEur 2.2.40 Bruker Optik GmbH


Conclusion Chapt. 4

4.9 C onclusion

We believe, that for Michelson-type FT instruments (e.g.: Bruker


MATRIX series, Bruker VECTOR series, Bomem BM160 series,
Nicolet Antaris series, Perkin Elmer IdentiCheck series) using
water vapor for the wavelength uncertainty test is the most optimal
solution available for both diffuse reflection and transmission mea-
surements.

Due to the Connes' advantage only a single absorption peak is


required for the test.

The water vapor absorbance bands are very sharp and allow deter-
mination of the position to a very high accuracy.

For a Bruker MATRIX spectrometer, for example, the wavelength


uncertainty test is specified with a maximum deviation of 0.1cm-1.
A higher deviation would be regarded as failing the test. This limit is
much tighter than the requirements by USP (tolerances of 4cm-1).

Bruker Optik GmbH OVP for PhEur 2.2.40 49


Chapt. 4 Appendix - Wavelength Uncertainty Test us-

50 OVP for PhEur 2.2.40 Bruker Optik GmbH


Index Wavelength Reproducibilit 21
Wavelength Reproducibility 5, 30
Wavelength Uncertainty 5, 18, 27,
36, 39

C
Connes’ Advantage 48

H
High Flux Noise 4

I
IVU 35

L
Laser Wavenumber 9
Low Flux Noise 4

P
Photometric Linearity 14, 23, 34
Photometric Noise 17, 25, 35
Printing Reports 33

R
Reference Standards 4
Reflection Measurement 13
Report 33
Run Tests 31

T
Test Setup 3
Transmission Measurement 22

U
USP Requirements 41

W
Water Vapor Absorbance 46
Wavelength 45

Bruker Optik GmbH OVP for PhEur 2.2.40


Index

OVP for PhEur 2.2.40 Bruker Optik GmbH

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