ASTM D6562-06(2011)
(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
SIGNIFICANCE AND USE
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.
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 (4-7).
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 (8). The Occupational Safety & Health Administration of the U.S. Department of Labor (OSHA) has not listed a permissible exposure limit (PEL) for HDI (9).
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 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 μg of monomeric HDI/2.0 mL of desorption solution, which corresponds to concentrations equivalent to 0.0004 to 0.075 mg/m3 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 0.012 μg/2 mL of desorption solution and as 0.008 μg/2 mL, using the fluorescence detector. These limits correspond to 0.0008 mg/m3 and 0.0005 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 μg/2 mL is close to the expected detection limit.
1.6 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 regu...
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NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
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Designation:D6562–06 (Reapproved 2011)
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 D6562; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision.Anumber in parentheses indicates the year of last reapproval.A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope validated from 0.006 to 1.12 µg of monomeric HDI/2.0 mLof
desorption solution, which corresponds to concentrations
1.1 This test method covers the determination of gaseous
equivalent to 0.0004 to 0.075 mg/m of HDI based on a 15-L
hexamethylene diisocyanate (HDI) in air samples collected
air sample. Those concentrations correspond to a range of
from workplace and ambient atmospheres. The method de-
vaporphaseconcentrationsfrom0.06ppb(V)to11ppb(V)and
scribed in this test method collects separate fractions. One
cover the established threshold limit value (TLV) value of 5
fractionwillbedominatedbyvapor,andtheotherfractionwill
ppb(V).
be dominated by aerosol. It is not known at the present time
1.5 The quantification limit for the monomeric HDI, using
whether this represents a perfect separation of vapor and
the UV detection, has been established as 0.012 µg/2 mL of
aerosol, and in any case, there are not separate exposure
desorption solution and as 0.008 µg/2 mL, using the fluores-
standards for vapor and aerosol. Therefore, in comparing the
cence detector. These limits correspond to 0.0008 mg/m and
results for isocyanate against a standard, results from the two
0.0005 mg/m respectively for an air sampled volume of 15 L.
fractions should be combined to give a single total value. The
Thesevaluesareequaltotentimesthestandarddeviation(SD)
reason for splitting the sample into two fractions is to increase
obtained from ten measurements carried out on a standard
analytic sensitivity for the vapor fraction and also to give the
solution in contact with the GFF, whose concentration of 0.02
hygienist or ventilation engineer some information concerning
µg/2 mL is close to the expected detection limit.
the likely state of the isocyanate species. The analyses of the
1.6 This standard does not purport to address all of the
twofractionsaredifferent,andareprovidedinseparate,linked,
safety concerns, if any, associated with its use. It is the
standards to avoid confusion. This test method is principally
responsibility of the user of this standard to establish appro-
used to determine short term exposure (15 min) of HDI in
priate safety and health practices and determine the applica-
workplaceenvironmentsforpersonalmonitoringorinambient
bility of regulatory limitations prior to use. See Section 9 for
air.Theanalysisoftheaerosolfractionisperformedseparately,
additional hazards.
as described in Test Method D6561.
1.2 Differential air sampling is performed with a segregat-
2. Referenced Documents
ing device. The vapor fraction is collected on a glass fiber
2.1 ASTM Standards:
filter (GFF) impregnated with 9-(N-methylaminomethyl) an-
D1193 Specification for Reagent Water
thracene (MAMA).
D1356 Terminology Relating to Sampling and Analysis of
1.3 Theanalysisofthegaseousfractionisperformedwitha
Atmospheres
high performance liquid chromatograph (HPLC) equipped
D1357 Practice for Planning the Sampling of the Ambient
with ultraviolet (UV) and fluorescence detectors.
Atmosphere
1.4 The range of application of this test method, using UV
D5337 Practice for Flow Rate Calibration of Personal
and fluorescence detectors both connected in serial, has been
Sampling Pumps
D6561 Test Method for Determination of Aerosol Mono-
meric and Oligomeric Hexamethylene Diisocyanate (HDl)
This test method is under the jurisdiction of ASTM Committee D22 on Air
inAir with (Methoxy-2−phenyl-1) Piperazine (MOPIP) in
Quality and is the direct responsibility of Subcommittee D22.04 on WorkplaceAir
the Workplace
Quality.
Current edition approved Oct. 1, 2011. Published October 2011. Originally
2.2 Other Standard:
approved in 2000. Last previous edition approved in 2006 as D6562-06. DOI:
10.1520/D6562-06R11.
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 toASTM 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.
D6562–06 (2011)
Sampling Guide for Air Contaminants in the Workplace many industrial processes, and its low detection limit with the
concentrations often found in the working area.
3. Terminology
6. Interferences
3.1 Fordefinitionsoftermsusedinthistestmethod,referto
Terminology D1356. 6.1 Any substances, including strong oxidizing agents, that
canreactwiththeMAMAreagentimpregnatedontheGFFcan
4. Summary of Test Method
affect the sampling efficiency.
6.2 Any compound that has the same retention time as the
4.1 Vapor and aerosol fractions are sampled simultaneously
hexamethylenediisocyanate9-(N-methylaminomethyl)anthra-
by using a segregating sampling device. The aerosols are
cene (HDIU) derivative and contributes to the UV signal is an
collected on a polyterafluoroethylene (PTFE) filter while the
interference. Chromatographic conditions can sometimes be
gaseousfractionisbeingadsorbedonthesecondfiltermadeof
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 D6561.
4.3 Diisocyanates present as vapors react with the second-
7. Apparatus
ary amine function of the MAMA, impregnated on the GFF to
form a urea derivative (1,2) as shown in Fig. 1. 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 through the sam-
pling device for a period of at least 4 h.
7.1.2 Double Filter Sampling Device, 37 mm in diameter,
FIG. 1
three-piece personal monitor, plastic holder loaded with a
PTFEfilterclosetothemouth,followedbyaGFFimpregnated
with MAMA and by a plastic back-up pad. The GFF is
DesorptionoftheGFFisdonebyusingasolutionmixtureof
impregnatedwithanamountofMAMAintherangefrom0.07
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 D5337.
followed by UV (254 nm) and fluorescence detectors (254-nm
7.2 Analytical Equipment:
excitation 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 excitation) 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 by 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)hasadoptedathresholdlimitvalue-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
Thesolesourceofsupplyoftheapparatusknowntothecommitteeatthistime
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
Theboldfacenumbersinparenthesesrefertothelistofreferencesattheendof consideration at a meeting of the responsible technical committee, which you may
this standard. attend.
D6562–06 (2011)
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 sol-
size polyamide filters, or any equivalent method.
vents. 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 D1357 and D5337 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.Placethefilterholderpointingdownward,ifpossible,at
Other grades may be used, provided it is first ascertained that
anoptimumangleof45°fromhorizontalinthebreathingzone
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
supporttolocatethesamplerinageneralroomareaataheight
D1193, 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-Lvolumetric 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 mLof
8.10).
MOPIP derivatization solution (see Test Method D6561), 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 D6561).
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 75% (v/v) of 10.8 Send the jars and the cassettes to be analyzed to the
laboratory. Keep away from light.
acetonitrile (CH CN) (see 8.3) and 25% (v/v) of buffer (see
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-
PracticeD5337.Calibratethepumpbeforeandaftersampling.
methylaminomethyl) Anthracene Derivative (HDIU) (see
If the flow rate after the sampling differs by more than 5%
11.2.1).
from the flow rate be
...
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