ASTM D6562-00
(Test Method)Standard Test Method for Determination of Gaseous Hexamethylene Diisocyanate (HDI) in Air with 9-(N-methylaminomethyl) Anthracene Method (MAMA) in the Workplace
Standard Test Method for Determination of Gaseous Hexamethylene Diisocyanate (HDI) in Air with 9-(N-methylaminomethyl) Anthracene Method (MAMA) in the Workplace
SCOPE
1.1 This test method covers the determination of gaseous 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 aerosol fraction is performed separately, as described in Test Method D6561.
1.2 Differential air sampling is performed with a segregating device. The vapor fraction is collected on a glass fiber filter (GFF) impregnated with 9-(N-methylaminomethyl) anthracene (MAMA).
1.3 The analysis of the gaseous fraction is performed with a high performance liquid chromatograph (HPLC) equipped with ultraviolet (UV) and fluorescence detectors.
1.4 The range of application of this test method, using UV and fluorescence detectors both connected in serial, has been validated from 0.006 to 1.12 g of monomeric HDI/2.0 mL of desorption solution, which corresponds to concentrations equivalent to 0.0004 to 0.075 mg/m 3 of HDI based on a 15-L air sample. Those concentrations correspond to a range of vapor phase concentrations from 0.06 ppb(V) to 11 ppb(V) and cover the established threshold limit value (TLV) value of 5 ppb(V).
1.5 The quantification limit for the monomeric HDI, using the UV detection, has been established as 0.016 g/2 mL of desorption solution and as 0.009 g/2 mL, using the fluorescence detector. These limits correspond to 0.001 mg/m3 and 0.0006 mg/m3 respectively for an air sampled volume of 15 L. These values are equal to ten times the standard deviation (SD) obtained from ten measurements carried out on a standard solution in contact with the GFF, whose concentration of 0.02 g/2 mL is close to the expected detection limit.
1.6This 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.
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Designation:D6562–00
Standard Test Method for
Determination of Gaseous Hexamethylene Diisocyanate
(HDI) in Air with 9-(N-methylaminomethyl) Anthracene
Method (MAMA) in the Workplace
This standard is issued under the fixed designation D 6562; 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 (e) indicates an editorial change since the last revision or reapproval.
1. Scope desorption solution, which corresponds to concentrations
equivalent to 0.0004 to 0.075 mg/m of HDI based on a 15-L
1.1 This test method covers the determination of gaseous
air sample. Those concentrations correspond to a range of
hexamethylene diisocyanate (HDI) in air samples collected
vaporphaseconcentrationsfrom0.06ppb(V)to11ppb(V)and
from workplace and ambient atmospheres. The method de-
cover the established threshold limit value (TLV) value of 5
scribed in this test method collects separate fractions. One
ppb(V).
fraction will be dominated by vapor, and the other fraction will
1.5 The quantification limit for the monomeric HDI, using
be dominated by aerosol. It is not known at the present time
the UV detection, has been established as 0.016 µg/2 mL of
whether this represents a perfect separation of vapor and
desorption solution and as 0.009 µg/2 mL, using the fluores-
aerosol, and in any case, there are not separate exposure
cence detector. These limits correspond to 0.001 mg/m and
standards for vapor and aerosol. Therefore, in comparing the
0.0006 mg/m respectively for an air sampled volume of 15 L.
results for isocyanate against a standard, results from the two
These values are equal to ten times the standard deviation (SD)
fractions should be combined to give a single total value. The
obtained from ten measurements carried out on a standard
reason for splitting the sample into two fractions is to increase
solution in contact with the GFF, whose concentration of 0.02
analytic sensitivity for the vapor fraction and also to give the
µg/2 mL is close to the expected detection limit.
hygienist or ventilation engineer some information concerning
1.6 This standard does not purport to address all of the
the likely state of the isocyanate species. The analyses of the
safety concerns, if any, associated with its use. It is the
twofractionsaredifferent,andareprovidedinseparate,linked,
responsibility of the user of this standard to establish appro-
standards to avoid confusion. This test method is principally
priate safety and health practices and determine the applica-
used to determine short term exposure (15 min) of HDI in
bility of regulatory limitations prior to use. See Section 9 for
workplace environments for personal monitoring or in ambient
additional hazards.
air.Theanalysisoftheaerosolfractionisperformedseparately,
as described in Test Method D 6561.
2. Referenced Documents
1.2 Differential air sampling is performed with a segregat-
2 2.1 ASTM Standards:
ing device. The vapor fraction is collected on a glass fiber
D 1193 Specification for Reagent Water
filter (GFF) impregnated with 9-(N-methylaminomethyl) an-
D 1356 Terminology Relating to Sampling and Analysis of
thracene (MAMA).
Atmospheres
1.3 The analysis of the gaseous fraction is performed with a
D 1357 Practice for Planning the Sampling of the Ambient
high performance liquid chromatograph (HPLC) equipped
Atmosphere
with ultraviolet (UV) and fluorescence detectors.
D 5337 Practice for Flow Rate for Calibration of Personal
1.4 The range of application of this test method, using UV
Sampling Pumps
and fluorescence detectors both connected in serial, has been
D 6561 Test Method for Determination of Aerosol Mono-
validated from 0.006 to 1.12 µg of monomeric HDI/2.0 mL of
meric and Oligomeric Hexamethylene Diisocyanate (HDI)
in Air with (Methoxy-2 phenyl-1) Piperazine (MOPIP) in
This test method is under the jurisdiction of ASTM Committee D22 on the Workplace
Sampling and Analysis of Atmospheres and is the direct responsibility of Subcom-
mittee D22.04 on Workplace Atmospheres.
Current edition approved June 10, 2000. Published August 2000.
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.
D6562–00
2.2 Other Standard: many industrial processes, and its low detection limit with the
Sampling Guide for Air Contaminants in the Workplace concentrations often found in the working area.
3. Terminology 6. Interferences
3.1 For definitions of terms used in this test method, refer to 6.1 Any substances, including strong oxidizing agents, that
Terminology D 1356. canreactwiththeMAMAreagentimpregnatedontheGFFcan
affect the sampling efficiency.
4. Summary of Test Method
6.2 Any compound that has the same retention time as the
4.1 Vapor and aerosol fractions are sampled simultaneously hexamethylene diisocyanate 9-(N-methylaminomethyl) an-
by using a segregating sampling device. The aerosols are
thracene (HDIU) derivative and contributes to the UVsignal is
collected on a polyterafluoroethylene (PTFE) filter while the an interference. Chromatographic conditions can sometimes be
gaseous fraction is being adsorbed on the second filter made of
changed to eliminate an interference. The response factor (RF)
glass fiber impregnated with MAMA. ratio from the UV and fluorescence detectors gives a good
4.2 The analysis of the oligomer in the aerosol fraction is
indication to the analyst about the possibility of an interfer-
performed separately in accordance with the procedure de- ence.
scribed in Test Method D 6561.
7. Apparatus
4.3 Diisocyanates present as vapors react with the second-
ary amine function of the MAMA, impregnated on the GFF to
7.1 Sampling Equipment:
form a urea derivative (1,2) as shown in Fig. 1. 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 through the sam-
pling device for a period of at least 4 h.
7.1.2 Double Filter Sampling Device, 37 mm in diameter,
three-piece personal monitor, plastic holder loaded with a
FIG. 1
PTFEfilterclosetothemouth,followedbyaGFFimpregnated
with MAMA and by a plastic back-up pad. The GFF is
DesorptionoftheGFFisdonebyusingasolutionmixtureof
impregnated with an amount of MAMAin the range from 0.07
67 % N,N-dimethylformamide and 33 % of a 30:70 buffer-
to 0.25 mg.
acetonitrile mixture. Monomeric and oligomeric diisocyanates
7.1.3 Flow Measuring Device, used in accordance with
are separated by using a reversed phase HPLC column,
Practice D 5337.
followed by UV (254 nm) and fluorescence detectors (254-nm
7.2 Analytical Equipment:
exitation and 412-nm emission) in series (3).
7.2.1 Liquid Chromatograph, an HPLC, equipped with a
4.4 Concentration of urea derivative contained in the
UV (254-nm wavelength) and fluorescence detectors (412-nm
samples is calculated by using an external standard of the
emission and 254-nm exitation) and equipped with an auto-
appropriate urea derivative.
matic or manual sampling port injection.
7.2.2 Liquid Chromatographic Column, an HPLC stainless
5. Significance and Use
steel column, capable of separating the urea derivatives. This
5.1 HDI is mostly used in the preparation of paints. For the
test method recommends a 150 3 3.2-mm internal diameter
last ten years, the use of isocyanates and their industrial needs
stainlesssteelcolumnpackedwith3µmC-18,oranequivalent
have been in constant growth.
column.
5.2 Diisocyanates and polyisocyanates are irritants to skin,
7.2.3 Electronic Integrator, or any other effective method
eyes, and mucous membranes. They are recognized to cause
for determining peak area counts.
respiratory allergic sensitization, asthmatic bronchitis, and
7.2.4 Analytical Balance, with a precision of 6 0.0001 g.
acute respiratory intoxication (4-7).
7.2.5 Microsyringes and Pipets—Microsyringes are used in
5.3 The American Conference of Governmental Industrial
thepreparationofureaderivativesandstandards.Anautomatic
Hygienists (ACGIH) has adopted a threshold limit value - time
pipet, or any equivalent equipment, is required for sample
weighted average (TLV - TWA) of 0.005 ppm (V) or 0.034
preparation.
mg/m (8). The Occupational Safety & Health Administration
7.2.6 pH Meter, or any equivalent device capable of assay-
of the U.S. Department of Labor (OSHA) has not listed a
ing a pH range between 2.5 and 7.
permissible exposure limit (PEL) for HDI (9).
7.2.7 Three-neck Flask, for the synthesis of the HDIU
5.4 Due to its low LOD and low required volume (15 L),
standard (see 8.13).
thistestmethodiswellsuitedformonitoringofrespiratoryand
7.2.8 Magnetic Stirrer, or any other equivalent device.
other problems related to diisocyanates and polyisocyanates.
Its short sampling times are compatible with the duration of
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 (10). 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.
D6562–00
7.2.9 Glass Jars, 30 mL, and lids, capable of receiving 37 9. Hazards
mm filters, used for sample desorption.
9.1 Warning—Diisocyanates are potentially hazardous
7.2.10 Reciprocating Shaker, or any other equivalent de-
chemicals and are extremely reactive. Refer to material safety
vice.
data sheets for reagents.
7.2.11 Vacuum Filtration System, filter with 0.22-µm pore
9.2 Warning—Avoid exposure to diisocyanate and solvents.
size polyamide filters, or any equivalent method.
Sample and standard preparations should be done in an
7.2.12 Syringe Operated Filter Unit, syringes with polyvi-
efficient operating hood. For remedial statement, see Ref (11).
nylidene fluoride 0.22-µm pore size filter unit, or any equiva-
9.3 Warning—Avoid skin contact with isocyanates and all
lent method.
solvents. N,N-Dimethylformamide is highly toxic. Chronic
7.2.13 Injection Vials, 1.5 mL vials with PTFE-coated
effects include damage to liver and kidneys. See Ref (12).
septums.
9.4 Warning—Wear safety glasses at all times and other
7.2.14 Bottle, amber bottle with cap and PTFE coated
laboratory protective equipment if necessary.
septum for conservation of stock and standard solutions of
10. Sampling
HDIU, or any equivalent equipment.
10.1 Refer to Practices D 1357 and D 5337 for general
information on sampling.
8. Reagents and Materials
10.2 This test method recommends sampling in accordance
8.1 Purity of Reagents—Reagent grade chemicals shall be
with the method described in the Ref (10, 11, 13).
usedinalltests.Allreagentsshallconformtothespecifications
10.3 Equip the worker, whose exposure is to be evaluated,
of the Committee on Analytical Reagents of the American
with a filter holder connected to a belt-supported sampling
Chemical Society where such specifications are available.
pump. Place the filter holder pointing downward, if possible, at
Other grades may be used, provided it is first ascertained that
an optimum angle of 45° from horizontal in the breathing zone
the reagent is of sufficiently high purity to permit its use
of the worker. Draw air through the sampling device and
without lessening the accuracy of the determination.
collect 15 L at a rate of approximately 1.0 L/min.
8.2 Purity of Water—Unless otherwise indicated, water
10.4 For stationary monitoring, use a tripod or any other
shall be reagent water as defined by Type 2 of Specification
support to locate the sampler in a general room area at a height
D 1193, HPLC grade.
equivalent to the breathing zone.
8.3 Acetonitrile (CH CN), HPLC grade.
10.5 A field blank is used to monitor contamination during
8.4 Buffer—Transfer 30 mLof triethylamine (see 8.14) into
the combined sampling, transportation, and storage process.
a 1-L volumetric flask, and dilute to volume with HPLC grade
Open the field blanks in the environment to be sampled, and
water. Acidify the solution to pH = 3 with phosphoric acid
immediately close them. Process field blanks in the same
(H PO ) (see 8.11). Filter the buffer under vacuum with a
3 4
manner as samples. Submit at least one field blank for every
0.22-µm pore size filter.
ten samples.
8.5 Desorption Solution, a solvent mixture of 67 % (v/v) of
10.6 Immediately after sampling, open the cassette, with-
dimethylformamide(see8.7)and33 %(v/v)mobilephase(see
draw the PTFE filter, place it in a glass jar containing 5 mL of
8.10).
MOPIP derivatization solution (see Test Method D 6561), and
8.6 Dichloromethane, reagent grade.
close the jar. This filter is used to analyze the aerosol fraction
8.7 N,N-Dimethylformamide, reagent grade.
of diisocyanates (see Test Method D 6561).
8.8 Helium (He), high purity.
10.7 Close the cassette, leaving the GFF and the plastic pad
8.9 9-(N-Methylaminomethyl) Anthracene (MAMA) (F.W.
support. The GFF is used to analyze the vapor fraction of
221.31), 99 % purity.
diisocyanates.
8.10 Mobile Phase, a solvent mixture of 70 % (v/v) of
10.8 Send the jars and the cassettes to be analyzed to the
acetonitrile (CH CN) (see 8.3) and 30 % (v/v) of buffer (see
laboratory. Keep away from light.
8.4).
11. Calibration and Standardization
8.11 Phosphoric Acid (H PO ), reagent grade
3 4
11.1 Sample Pump Calibration—Calibrate the sampling
8.12 Hexamethylene Diisocyanate (HDI), (F.W. 168), 98 %
pump (see 7.1.1) with a cassette (see 7.1.2) between the pump
purity.
and the flow measuring device (see 7.1.3), in accordance with
8.13 Hexamethylene Diisocyanate 9-(N-
PracticeD 5337.Calibratethepumpbeforeandaftersampling.
methylaminomethyl) Anthracene Derivative (HDIU) (see
If the flow rate after the sampling
...
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