ASTM D6561-06(2016)
(Test Method)Standard Test Method for Determination of Aerosol Monomeric and Oligomeric Hexamethylene Diisocyanate (HDl) in Air with (Methoxy-2–phenyl-1) Piperazine (MOPIP) in the Workplace
Standard Test Method for Determination of Aerosol Monomeric and Oligomeric Hexamethylene Diisocyanate (HDl) in Air with (Methoxy-2–phenyl-1) Piperazine (MOPIP) in the Workplace
SIGNIFICANCE AND USE
5.1 HDI is mostly used in the preparation of paints. For the last ten years, the use of isocyanates and their industrial needs have been in constant growth.
5.2 Diisocyanates and polyisocyanates are irritants to skin, eyes, and mucous membranes. They are recognized to cause respiratory allergic sensitization, asthmatic bronchitis, and acute respiratory intoxication (3-6).
5.3 The American Conference of Governmental Industrial Hygienists (ACGIH) has adopted a threshold limit value - time weighted average (TLV – TWA) of 0.005 ppm (V) or 0.034 mg/m3 for monomeric HDI (7). The Occupational Safety & Health Administration of the U.S. Department of Labor (OSHA) has not listed a permissible exposure limit (PEL) for HDI (8).
5.4 Due to its low LOD and low required volume (15 L), this test method is well suited for monitoring of respiratory and other problems related to diisocyanates and polyisocyanates. Its short sampling times are compatible with the duration of many industrial processes, and its low detection limit with the concentrations often found in the working area.
SCOPE
1.1 This test method covers the determination of aerosol hexamethylene diisocyanate (HDI) in air samples collected from workplace and ambient atmospheres. The method described in this test method collects separate fractions. One fraction will be dominated by vapor, and the other fraction will be dominated by aerosol. It is not known at the present time whether this represents a perfect separation of vapor and aerosol, and in any case, there are not separate exposure standards for vapor and aerosol. Therefore, in comparing the results for isocyanate against a standard, results from the two fractions should be combined to give a single total value. The reason for splitting the sample into two fractions is to increase analytic sensitivity for the vapor fraction and also to give the hygienist or ventilation engineer some information concerning the likely state of the isocyanate species. The analyses of the two fractions are different, and are provided in separate, linked, standards to avoid confusion. This test method is principally used to determine short term exposure (15 min) of HDI in workplace environments for personal monitoring or in ambient air. The analysis of the vapor fraction is performed separately, as described in Test Method D6562.
1.2 Differential air sampling is performed with a segregating device.2 The aerosol fraction is collected on a polytetrafluoroethylene (PTFE) filter.
1.3 Immediately after sampling, the PTFE filter is transferred into a jar containing a (methoxy-2 phenyl-1) piperazine (MOPIP) solution in toluene.
1.4 The analysis of the aerosol fraction is performed by using a high performance liquid chromatograph (HPLC) equipped with an ultraviolet (UV) detector. The range of application of the test method has been validated from 0.052 to 1.04 μg of monomeric HDI/mL, which corresponds, based on a 15 L air sample, to concentrations from 0.004 to 0.070 mg/m3 of HDI. Those concentrations correspond to a range of aerosol phase concentrations from 0.5 ppb (V) to 10 ppb (V) and cover the established threshold limit valve (TLV) value of 5 ppb (V).
1.5 The quantification limit for the monomeric HDI is 0.041 μg per mL, which corresponds to 0.003 mg/m3 for a 15 L sampled air volume. This value is equivalent to ten times the standard deviation obtained from ten measurements carried out on a standard solution in contact with the PTFE filter whose concentration of 0.1 μg/mL is close to the expected detection limit.
1.6 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
1.7 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 appropriate safety and health practices and determine the applicability of regula...
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Designation: D6561 − 06 (Reapproved 2016)
Standard Test Method for
Determination of Aerosol Monomeric and Oligomeric
Hexamethylene Diisocyanate (HDl) in Air with (Methoxy-
2–phenyl-1) Piperazine (MOPIP) in the Workplace
This standard is issued under the fixed designation D6561; 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 equipped with an ultraviolet (UV) detector. The range of
application of the test method has been validated from 0.052 to
1.1 This test method covers the determination of aerosol
1.04 µg of monomeric HDI/mL, which corresponds, based on
hexamethylene diisocyanate (HDI) in air samples collected
a15Lairsample,toconcentrationsfrom0.004to0.070mg/m
from workplace and ambient atmospheres. The method de-
of HDI. Those concentrations correspond to a range of aerosol
scribed in this test method collects separate fractions. One
phase concentrations from 0.5 ppb (V) to 10 ppb (V) and cover
fraction will be dominated by vapor, and the other fraction will
the established threshold limit valve (TLV) value of 5 ppb (V).
be dominated by aerosol. It is not known at the present time
whether this represents a perfect separation of vapor and 1.5 The quantification limit for the monomeric HDI is 0.041
aerosol, and in any case, there are not separate exposure µg per mL, which corresponds to 0.003 mg/m fora15L
standards for vapor and aerosol. Therefore, in comparing the sampled air volume. This value is equivalent to ten times the
results for isocyanate against a standard, results from the two standard deviation obtained from ten measurements carried out
fractions should be combined to give a single total value. The on a standard solution in contact with the PTFE filter whose
reason for splitting the sample into two fractions is to increase concentration of 0.1 µg/mL is close to the expected detection
analytic sensitivity for the vapor fraction and also to give the limit.
hygienist or ventilation engineer some information concerning
1.6 The values stated in SI units are to be regarded as
the likely state of the isocyanate species. The analyses of the
standard. No other units of measurement are included in this
twofractionsaredifferent,andareprovidedinseparate,linked,
standard.
standards to avoid confusion. This test method is principally
1.7 This standard does not purport to address all of the
used to determine short term exposure (15 min) of HDI in
safety concerns, if any, associated with its use. It is the
workplace environments for personal monitoring or in ambient
responsibility of the user of this standard to establish appro-
air. The analysis of the vapor fraction is performed separately,
priate safety and health practices and determine the applica-
as described in Test Method D6562.
bility of regulatory limitations prior to use. See Section 9 for
1.2 Differential air sampling is performed with a segregat-
additional hazards.
ing device. The aerosol fraction is collected on a polytetra-
1.8 This international standard was developed in accor-
fluoroethylene (PTFE) filter.
dance with internationally recognized principles on standard-
ization established in the Decision on Principles for the
1.3 Immediately after sampling, the PTFE filter is trans-
Development of International Standards, Guides and Recom-
ferred into a jar containing a (methoxy-2 phenyl-1) piperazine
mendations issued by the World Trade Organization Technical
(MOPIP) solution in toluene.
Barriers to Trade (TBT) Committee.
1.4 The analysis of the aerosol fraction is performed by
using a high performance liquid chromatograph (HPLC)
2. Referenced Documents
2.1 ASTM Standards:
This test method is under the jurisdiction of ASTM Committee D22 on Air
D1193 Specification for Reagent Water
Quality and is the direct responsibility of Subcommittee D22.04 on Workplace Air
D1356 Terminology Relating to Sampling and Analysis of
Quality.
Current edition approved Nov. 1, 2016. Published November 2016. Originally
Atmospheres
approved in 2000. Last previous edition approved in 2011 as D6561 – 06 (2011).
DOI: 10.1520/D6561-06R16.
The sampling device for isocyanates is covered by a patent held by Jacques
Lesage et al, IRSST, 505 De Maisonneuve Blvd. West, Montreal, Quebec, Canada. For referenced ASTM standards, visit the ASTM website, www.astm.org, or
If you are aware of an alternative to this patented item, please provide this contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
information to ASTM Headquarters. Your comments will receive careful consider- Standards volume information, refer to the standard’s Document Summary page on
ation at a meeting of the responsible technical committee, which you may attend. the ASTM website.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D6561 − 06 (2016)
5.3 The American Conference of Governmental Industrial
Hygienists (ACGIH) has adopted a threshold limit value - time
weighted average (TLV – TWA) of 0.005 ppm (V) or 0.034
mg/m for monomeric HDI (7). The Occupational Safety &
FIG. 1 MOPIP Solution
Health Administration of the U.S. Department of Labor
(OSHA) has not listed a permissible exposure limit (PEL) for
HDI (8).
D1357 Practice for Planning the Sampling of the Ambient
5.4 Due to its low LOD and low required volume (15 L),
Atmosphere
thistestmethodiswellsuitedformonitoringofrespiratoryand
D5337 Practice for Flow RateAdjustment of Personal Sam-
other problems related to diisocyanates and polyisocyanates.
pling Pumps
Its short sampling times are compatible with the duration of
D6562 Test Method for Determination of Gaseous Hexam-
many industrial processes, and its low detection limit with the
ethylene Diisocyanate (HDI) in Air with 9-(N-
concentrations often found in the working area.
methylaminomethyl)Anthracene Method (MAMA) in the
Workplace
4 6. Interferences
2.2 Other Standard:
Sampling Guide for Air Contaminants in the Workplace 6.1 Any substance, including strong oxidizing agents, that
can be deposited on the PTFE filter and react with MOPIP
3. Terminology
reagent can affect the analysis efficiency.
3.1 Definitions:
6.2 Any compound that has the same retention time as the
3.1.1 For definitions of terms used in this test method, refer
HDI-MOPIP derivative and contributes to UV response is an
to Terminology D1356.
interference. Chromatographic conditions can sometimes be
changed to eliminate an interference.
4. Summary of Test Method
7. Apparatus
4.1 Vapor and aerosol fractions are sampled simultaneously
by using a segregating sampling device. The aerosols are
7.1 Sampling Equipment:
collected on PTFE filter while the gaseous fraction is being
7.1.1 Personal Sampling Pump, equipped with a flow-
adsorbed on a second filter made of glass fiber, impregnated
monitoring device (rotameter, critical orifice) or a constant-
with a 9-(N-methylaminomethyl) anthracene (MAMA).
flow device capable of drawing 1.0 L/min of air through the
sampling device for a period of at least 4 h.
4.2 The analysis of the monomer in the gaseous fraction is
performed separately in accordance with the procedure de- 7.1.2 Double Filter Sampling Device, 37 mm in diameter,
three-piece personal monitor, plastic holder loaded with a
scribed in Test Method D6562.
PTFE filter close to the mouth, followed by a glass fiber filter
4.3 Diisocyanates present as aerosols are collected on the
(GFF) impregnated with MAMA and a plastic back-up pad.
PTFE filter and derivatized in a MOPIP solution (1, 2). See
The GFF is impregnated with an amount of MAMA in the
Fig. 1.
range from 0.07 to 0.25 mg.
4.3.1 The solution is then evaporated to dryness and
7.1.3 Flow Measuring Device, used in accordance with
redissolved, using the acetic anhydride solution (see 8.11).
Practice D5337.
Monomeric and oligomeric HDI are separated by using a
7.2 Analytical Equipment:
reversed phase HPLC column, and detection is made by using
7.2.1 Liquid Chromatograph, HPLC, equipped with a UV
an HPLC equipped with UV detection.
detector(242nmwavelength),connectedinserieswithadiode
4.4 Concentration of monomeric and oligomeric diisocya-
detector, and equipped with an automatic or manual sampling
nates contained in a sample is calculated by using an external
port injection.
standard of the monomeric HDI.
7.2.2 Liquid Chromatographic Column, an HPLC stainless
steel column, capable of separating the urea derivatives. This
5. Significance and Use
test method recommends a 150 by 3.2-mm internal diameter
5.1 HDI is mostly used in the preparation of paints. For the
stainless steel column packed with 3 µm C-18, or an equivalent
last ten years, the use of isocyanates and their industrial needs
column.
have been in constant growth.
7.2.3 Electronic Integrator, or any other effective method
5.2 Diisocyanates and polyisocyanates are irritants to skin,
for determining peak areas.
eyes, and mucous membranes. They are recognized to cause 7.2.4 Analytical Balance, with a precision of 60.0001 g.
respiratory allergic sensitization, asthmatic bronchitis, and
acute respiratory intoxication (3-6).
The sole source of supply of the apparatus known to the committee at this time
isOmegaSpecialtyInstrument,Chelmsford,MAandispreparedinaccordancewith
Available from Institut de recherche en sante et en securite du travail du Patent No. 4 961 916 (9). If you are aware of alternative suppliers, please provide
Quebec, Laboratory Division, Montreal, IRSST. this information to ASTM Headquarters. Your comments will receive careful
5 1
The boldface numbers in parentheses refer to the list of references at the end of consideration at a meeting of the responsible technical committee, which you may
this standard. attend.
D6561 − 06 (2016)
7.2.5 Microsyringes and Pipets—Microsyringes are used in 8.9 (Methoxy-2-phenyl-1) Piperazine (MOPIP), (F.W.
thepreparationofureaderivativesandstandards.Anautomatic 192.2). 98 % purity.
pipet, or any equivalent equipment, is required for sample
8.10 Mobile Phase, a solvent mixture of 60 % (v/v) acetoni-
preparation.
trile (see 8.5) and 40 % (v/v) buffer (see 8.6).
7.2.6 pH Meter, or any equivalent device capable of assay-
8.11 Redissolution Solution—Dilute 500 µL of acetic anhy-
ing a pH range between 2.5 and 7.
dride ( (CH CO) O) (see 8.4) to 100 mL with acetonitrile (see
3 2
7.2.7 Culture Tubes, 16 by 100 mm, disposable, in borosili-
8.5).
cate glass for evaporation of derivatized samples.
7.2.8 Glass Jars, 30 mL, and lids, capable of receiving
8.12 Sodium Acetate (NaC H O ), certified ACS.
2 3 2
37-mm filters, used for derivatization of samples.
8.13 Toluene, HPLC grade.
7.2.9 Vacuum Filtration System, filter 47 mm, with 0.22-µm
pore size polyamide filters, or any equivalent method.
9. Hazards
7.2.10 Syringe Operated Filter Unit, syringes with 4 mm,
9.1 Warning—Diisocyanates are potentially hazardous
polyvinylidene fluoride 0.22-µm pore size filter unit, or any
chemicals and are extremely reactive. Refer to material safety
equivalent device.
data sheets for reagents.
7.2.11 Injection Vials, 1.5-mL vials with PTFE-coated sep-
tums.
9.2 Warning—Avoid exposure to diisocyanate and sol-
7.2.12 Bottle, amber colored bottle with cap and PTFE-
vents. Sample and standard preparations should be done in an
coated septum for conservation of stock and diluted standard
efficient operating hood. For remedial statement, see Ref (10).
solutions of HDI.
9.3 Warning—Wear safety glasses at all times and other
7.2.13 Vacuum Evaporator, capable of heating to 55°C, or
laboratory protective equipment if necessary.
any equivalent device.
7.2.14 Vortex Movement Mixer, or any equivalent device.
10. Sampling
8. Reagents and Materials 10.1 Refer to Practice D1357 for general information on
sampling.
8.1 Purity of Reagents—Reagent grade chemicals shall be
usedinalltests.Allreagentsshallconformtothespecifications 10.2 This test method recommends sampling in accordance
with the method described in Refs (9-11).
of the Committee on Analytical Reagents of the American
Chemical Society where such specifications are available.
10.3 Equip the worker, whose exposure is to be evaluated,
Other grades may be used, provided it is first ascertained that
with a filter holder connected to a belt-supported sampling
the reagent is of sufficiently high purity to permit its use
pump. Place the filter holder pointing downward, if possible, at
without lessening the accuracy of the determination.
an optimum angle of 45° from horizontal in the breathing zone
8.2 Purity of Water—Unlessotherwiseindicated,watershall of the worker. Draw air through the sampling device, and
collect 15 L at a rate of approximately 1.0 L/min.
be reagent water as defined by Type 2 of Specification D1193,
HPLC grade.
10.4 For stationary monitoring, use a tripod or any other
support to locate the sampler in a general room area at a height
8.3 Acetic Acid, glacial (CH COOH), HPLC grade.
equivalent to the breathing zone.
8.4 Acetic Anhydride (CH CO) O), certified by American
3 2
Chemical Society (ACS). 10.5 A field blank is used to monitor contamination during
the combined sampling, transportation, and storage process.
8.5 Acetonitrile, HPLC grade.
Open the field blanks in the environment to be sampled and
8.6 Buffer—In a 1-L volumetric flask, dissolve 12.5 g
immediately close them. Process field blanks in the same
sodium acetate (NaC H O ) (see 8.12) in water and dilute to
2 3 2
manner as samples. Submit at least one field blank for every
volume. Add glacial acetic acid (CH COOH) (see 8.11)to
ten samples.
acidify to pH = 6.0. Under vacuum, filter the buffer with a
10.6 Immediately after sampling, open the cassette, with-
0.22-µm pore size filter.
draw the PTFE filter, place it in a glass jar containing 5 mL of
8.7 Derivatization Solution—Weigh 50 mg of MOPIP (see
MOPIPderivatization solution (see 8.7), and close the jar.This
8.9), and dilute to 500 mL in a volumetric flask with toluene
filter is used to analyze the aerosol fraction of diisocyanates.
(see 8.13). This solution is equivalent to 0.1 mg MOPIP/mL.
10.7 Close the cassette leaving the GFF and the plastic pad
8.8 Hexamethylene Diisocyanate (HDI), (F.W. 168), 98 %
support. The GFF is used to analyze the gaseous fraction of
purity.
diisocyanates (see Test Method D6562).
10.8 Send the jars and the cassettes to be analyzed to the
laboratory. Keep away from light.
Reagent Chemicals, American Chemical Society Specifications, American
Chemical Society, Washington, D.C. For suggestions on the testing of reagents
...
This document is not an ASTM standard and is intended only to provide the user of an ASTM standard an indication of what changes have been made to the previous version. Because
it may not be technically possible to adequately depict all changes accurately, ASTM recommends that users consult prior editions as appropriate. In all cases only the current version
of the standard as published by ASTM is to be considered the official document.
Designation: D6561 − 06 (Reapproved 2011) D6561 − 06 (Reapproved 2016)
Standard Test Method for
Determination of Aerosol Monomeric and Oligomeric
Hexamethylene Diisocyanate (HDl) in Air with (Methoxy-
2–phenyl-1) Piperazine (MOPIP) in the Workplace
This standard is issued under the fixed designation D6561; 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
1.1 This test method covers the determination of aerosol hexamethylene diisocyanate (HDI) in air samples collected from
workplace and ambient atmospheres. The method described in this test method collects separate fractions. One fraction will be
dominated by vapor, and the other fraction will be dominated by aerosol. It is not known at the present time whether this represents
a perfect separation of vapor and aerosol, and in any case, there are not separate exposure standards for vapor and aerosol.
Therefore, in comparing the results for isocyanate against a standard, results from the two fractions should be combined to give
a single total value. The reason for splitting the sample into two fractions is to increase analytic sensitivity for the vapor fraction
and also to give the hygienist or ventilation engineer some information concerning the likely state of the isocyanate species. The
analyses of the two fractions are different, and are provided in separate, linked, standards to avoid confusion. This test method is
principally used to determine short term exposure (15 min) of HDI in workplace environments for personal monitoring or in
ambient air. The analysis of the vapor fraction is performed separately, as described in Test Method D6562.
1.2 Differential air sampling is performed with a segregating device. The aerosol fraction is collected on a polytetrafluoro-
ethylene (PTFE) filter.
1.3 Immediately after sampling, the PTFE filter is transferred into a jar containing a (methoxy-2 phenyl-1) piperazine (MOPIP)
solution in toluene.
1.4 The analysis of the aerosol fraction is performed by using a high performance liquid chromatograph (HPLC) equipped with
an ultraviolet (UV) detector. The range of application of the test method has been validated from 0.052 to 1.04 μg of monomeric
HDI/mL, which corresponds, based on a 15 L air sample, to concentrations from 0.004 to 0.070 mg/m of HDI. Those
concentrations correspond to a range of aerosol phase concentrations from 0.5 ppb (V) to 10 ppb (V) and cover the established
threshold limit valve (TLV) value of 5 ppb (V).
1.5 The quantification limit for the monomeric HDI is 0.041 μg per mL, which corresponds to 0.003 mg/m for a 15 L sampled
air volume. This value is equivalent to ten times the standard deviation obtained from ten measurements carried out on a standard
solution in contact with the PTFE filter whose concentration of 0.1 μg/mL is close to the expected detection limit.
1.6 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
1.7 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 appropriate safety and health practices and determine the applicability of regulatory
limitations prior to use. See Section 9 for additional hazards.
2. Referenced Documents
2.1 ASTM Standards:
D1193 Specification for Reagent Water
D1356 Terminology Relating to Sampling and Analysis of Atmospheres
This test method is under the jurisdiction of ASTM Committee D22 on Air Quality and is the direct responsibility of Subcommittee D22.04 on Workplace Air Quality.
Current edition approved Oct. 1, 2011Nov. 1, 2016. Published October 2011November 2016. Originally approved in 2000. Last previous edition approved in 20062011
as D6561 – 06.D6561 – 06 (2011). DOI: 10.1520/D6561-06R11.10.1520/D6561-06R16.
The sampling device for isocyanates is covered by a patent held by Jacques Lesage et al, IRSST, 505 De Maisonneuve Blvd. West, Montreal, Quebec, Canada. If you
are aware of an alternative to this patented item, please provide this information to ASTM Headquarters. Your comments will receive careful consideration at a meeting of
the responsible technical committee, which you may attend.
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
D6561 − 06 (2016)
FIG. 1 MOPIP Solution
D1357 Practice for Planning the Sampling of the Ambient Atmosphere
D5337 Practice for Flow Rate Adjustment of Personal Sampling Pumps
D6562 Test Method for Determination of Gaseous Hexamethylene Diisocyanate (HDI) in Air with 9-(N-methylaminomethyl)
Anthracene Method (MAMA) in the Workplace
2.2 Other Standard:
Sampling Guide for Air Contaminants in the Workplace
3. Terminology
3.1 For definitions of terms used in this test method, refer to Terminology D1356Definitions:
3.1.1 For definitions of terms used in this test method, refer to Terminology D1356.
4. Summary of Test Method
4.1 Vapor and aerosol fractions are sampled simultaneously by using a segregating sampling device. The aerosols are collected
on PTFE filter while the gaseous fraction is being adsorbed on a second filter made of glass fiber, impregnated with a
9-(N-methylaminomethyl) anthracene (MAMA).
4.2 The analysis of the monomer in the gaseous fraction is performed separately in accordance with the procedure described
in Test Method D6562.
4.3 Diisocyanates present as aerosols are collected on the PTFE filter and derivatized in a MOPIP solution (1, 2). See Fig. 1.
4.3.1 The solution is then evaporated to dryness and redissolved, using the acetic anhydride solution (see 8.11). Monomeric and
oligomeric HDI are separated by using a reversed phase HPLC column, and detection is made by using an HPLC equipped with
UV detection.
4.4 Concentration of monomeric and oligomeric diisocyanates contained in a sample is calculated by using an external standard
of the monomeric HDI.
5. Significance and Use
5.1 HDI is mostly used in the preparation of paints. For the last ten years, the use of isocyanates and their industrial needs have
been in constant growth.
5.2 Diisocyanates and polyisocyanates are irritants to skin, eyes, and mucous membranes. They are recognized to cause
respiratory allergic sensitization, asthmatic bronchitis, and acute respiratory intoxication (3-6).
5.3 The American Conference of Governmental Industrial Hygienists (ACGIH) has adopted a threshold limit value - time
weighted average (TLV -– TWA) of 0.005 ppm (V) or 0.034 mg/m for monomeric HDI (7). The Occupational Safety & Health
Administration of the U.S. Department of Labor (OSHA) has not listed a permissible exposure limit (PEL) for HDI (8).
5.4 Due to its low LOD and low required volume (15 L), this test method is well suited for monitoring of respiratory and other
problems related to diisocyanates and polyisocyanates. Its short sampling times are compatible with the duration of many industrial
processes, and its low detection limit with the concentrations often found in the working area.
6. Interferences
6.1 Any substance, including strong oxidizing agents, that can be deposited on the PTFE filter and react with MOPIP reagent
can affect the analysis efficiency.
6.2 Any compound that has the same retention time as the HDI-MOPIP derivative and contributes to UV response is an
interference. Chromatographic conditions can sometimes be changed to eliminate an interference.
7. Apparatus
7.1 Sampling Equipment:
7.1.1 Personal Sampling Pump, equipped with a flow-monitoring device (rotameter, critical orifice) or a constant-flow device
capable of drawing 1.0 L/min of air through the sampling device for a period of at least 4 h.
Available from Institut de recherche en sante et en securite du travail du Quebec, Laboratory Division, Montreal, IRSST.
The boldface numbers in parentheses refer to the list of references at the end of this standard.
D6561 − 06 (2016)
7.1.2 Double Filter Sampling Device, 37 mm in diameter, three-piece personal monitor, plastic holder loaded with a PTFE filter
close to the mouth, followed by a glass fiber filter (GFF) impregnated with MAMA and a plastic back-up pad. The GFF is
impregnated with an amount of MAMA in the range from 0.07 to 0.25 mg.
7.1.3 Flow Measuring Device, used in accordance with Practice D5337.
7.2 Analytical Equipment:
7.2.1 Liquid Chromatograph, HPLC, equipped with a UV detector (242 nm wavelength), connected in series with a diode
detector, and equipped with an automatic or manual sampling port injection.
7.2.2 Liquid Chromatographic Column, an HPLC stainless steel column, capable of separating the urea derivatives. This test
method recommends a 150 by 3.2-mm internal diameter stainless steel column packed with 3 μm C-18, or an equivalent column.
7.2.3 Electronic Integrator, or any other effective method for determining peak areas.
7.2.4 Analytical Balance, with a precision of 60.0001 g.
7.2.5 Microsyringes and Pipets—Microsyringes are used in the preparation of urea derivatives and standards. An automatic
pipet, or any equivalent equipment, is required for sample preparation.
7.2.6 pH Meter, or any equivalent device capable of assaying a pH range between 2.5 and 7.
7.2.7 Culture Tubes, 16 by 100 mm, disposable, in borosilicate glass for evaporation of derivatized samples.
7.2.8 Glass Jars, 30 mL, and lids, capable of receiving 37-mm filters, used for derivatization of samples.
7.2.9 Vacuum Filtration System, filter 47 mm, with 0.22-μm pore size polyamide filters, or any equivalent method.
7.2.10 Syringe Operated Filter Unit, syringes with 4 mm, polyvinylidene fluoride 0.22-μm pore size filter unit, or any equivalent
device.
7.2.11 Injection Vials, 1.5-mL vials with PTFE-coated septums.
7.2.12 Bottle, amber colored bottle with cap and PTFE-coated septum for conservation of stock and diluted standard solutions
of HDI.
7.2.13 Vacuum Evaporator, capable of heating to 55°C, or any equivalent device.
7.2.14 Vortex Movement Mixer, or any equivalent device.
8. Reagents and Materials
8.1 Purity of Reagents—Reagent grade chemicals shall be used in all tests. All reagents shall conform to the specifications of
the Committee on Analytical Reagents of the American Chemical Society where such specifications are available. Other grades
may be used, provided it is first ascertained that the reagent is of sufficiently high purity to permit its use without lessening the
accuracy of the determination.
8.2 Purity of Water—Unless otherwise indicated, water shall be reagent water as defined by Type 2 of Specification D1193.,
HPLC grade.
8.3 Acetic Acid, glacial (CH COOH), HPLC grade.
8.4 Acetic Anhydride (CH CO) O), certified by American Chemical Society (ACS).
3 2
8.5 Acetonitrile, HPLC grade.
8.6 Buffer—In a 1-L volumetric flask, dissolve 12.5 g sodium acetate (NaC H O ) (see 8.12) in water and dilute to volume. Add
2 3 2
glacial acetic acid (CH COOH) (see 8.11) to acidify to pH = 6.0. Under vacuum, filter the buffer with a 0.22-μm pore size filter.
8.7 Derivatization Solution—Weigh 50 mg of MOPIP (see 8.9), and dilute to 500 mL in a volumetric flask with toluene (see
8.13). This solution is equivalent to 0.1 mg MOPIP/mL.
8.8 Hexamethylene Diisocyanate (HDI), (F.W. 168), 98 % purity.
8.9 (Methoxy-2-phenyl-1) Piperazine (MOPIP), (F.W. 192.2). 98 % purity.
8.10 Mobile Phase, a solvent mixture of 60 % (v/v) acetonitrile (see 8.5) and 40 % (v/v) buffer (see 8.6).
8.11 Redissolution Solution—Dilute 500 μL of acetic anhydride ( (CH CO) O) (see 8.4) to 100 mL with acetonitrile (see 8.5.)).
3 2
8.12 Sodium Acetate (NaC H O ), certified ACS.
2 3 2
8.13 Toluene, HPLC grade.
The sole source of supply of the apparatus known to the committee at this time is Omega Specialty Instrument, Chelmsford, MA and is prepared in accordance with
Patent No. 4 961 916 (9). If you are aware of alternative suppliers, please provide this information to ASTM Headquarters. Your comments will receive careful consideration
at a meeting of the responsible technical committee, which you may attend.
Reagent Chemicals, American Chemical Society Specifications, American Chemical Society, Washington, D.C. For suggestions on the testing of reagents not listed by
the American Chemical Society, see Analar Standards for Laboratory Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia and National
Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, MD.
D6561 − 06 (2016)
9. Hazards
9.1 Warning—Diisocyanates are potentially hazardous chemicals and are extremely reactive. Refer to material safety data
sheets for reagents.
9.2 Warning—Avoid exposure to diisocyanate and solvents. Sample and standard preparations should be done in an efficient
operating hood. For remedial statement, see Ref (10).
9.3 Warning—Wear safety glasses at all times and other laboratory protective equipment if necessary.
10. Sampling
10.1 Refer to Practice D1357 for general information on sampling.
10.2 This test method recommends sampling in accordance with the method described in RefRefs (9-11).
10.3 Equip the worker, whose exposure is to be evaluated, with a filter holder connected to a belt-supported sampling pump.
Place the filter holder pointing downward, if possible, at an optimum angle of 45° from horizontal in the breathing zone of the
worker. Draw air through the sampling device, and collect 15 L at a rate of approximately 1.0 L/min.
10.4 For stationary monitoring, use a tripod or any other support to locate the sampler in a general room area at a height
equivalent to the breathing zone.
10.5 A field blank is used to monitor contamination during the combined sampling, transportation, and storage process. Open
the field blanks in the environment to be sampled and immediately close them. Process field blanks in the same manner as samples.
Submit at least one field blank for every ten samples.
10.6 Immediately a
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