ASTM D6886-03(2009)

Standard Test Method for Speciation of the Volatile Organic Compounds (VOCs) in Low VOC Content Waterborne Air-Dry Coatings by Gas Chromatograpy

SIGNIFICANCE AND USE
In using Practice D 3960 to measure the regulatory VOC content of coatings, precision tends to be poor for low VOC content waterborne coatings because the VOC weight fraction is determined indirectly. The present method first identifies and then quantifies the weight fraction of individual VOCs directly in low VOC content waterborne air-dry coatings. The total VOC weight fraction can be obtained by adding the individual weight fraction values (Note 3).
Note 3—An effort is currently underway in California to consider changing mass-based VOC regulations for architectural coatings to reactivity-based VOC regulations. In California, reactivity based regulations have already been implemented for aerosol coatings, that is, MIR-indexed regulations (California Air Resources Board). Reactivity based regulations would require knowing the weight fractions of each individual volatile compound present in a coating.
SPME/GC makes it possible to identify very low levels of volatile compounds in a coating and could serve to make it possible to identify the presence of hazardous air pollutants (HAPs).
SCOPE
1.1 This test method is for the determination of the weight percent of individual volatile organic compounds in low VOC content waterborne latex air-dry coatings. The method is intended primarily for analysis of waterborne coatings in which the material VOC content is below 5 weight percent. The method has been used successfully with higher VOC content waterborne coatings.
1.2 This method may also be used to measure the exempt volatile organic compound content (acetone, methyl acetate, and p-chlorobezotrifluoride) of waterborne coatings. The methodology is virtually identical to that used in Test Method D 6133 and similar to that used in Test Method D 6438.  
1.3 Volatile compounds that are present at the 0.05 weight percent level or greater can be determined. Solid phase microextraction will detect volatile compounds at lower levels.
1.4 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
1.5 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.

General Information

• Status: Historical
• Publication Date: 31-May-2009
• ICS: 71.040.50 - Physicochemical methods of analysis
• Technical Committee: D01 - Paint and Related Coatings, Materials, and Applications
• Drafting Committee: D01.21 - Chemical Analysis of Paints and Paint Materials

Relations

• Replaces: ASTM D6886-03 - Standard Test Method for Speciation of the Volatile Organic Compounds (VOCs) in Low VOC Content Waterborne Air-Dry Coatings by Gas Chromatograpy
• Effective Date: 01-Jun-2009
• Replaced By: ASTM D6886-12 - Standard Test Method for Determination of the Individual Volatile Organic Compounds (VOCs) in Air-Dry Coatings by Gas Chromatography
• Effective Date: 01-May-2012
• Referred By: ASTM D7270-07(2021) - Standard Guide for Environmental and Performance Verification of Factory-Applied Liquid Coatings
• Effective Date: 01-Jun-2009
• Referred By: ASTM D6803-19 - Standard Practice for Testing and Sampling of Volatile Organic Compounds (Including Carbonyl Compounds) Emitted from Architectural Coatings Using Small-Scale Environmental Chambers
• Effective Date: 01-Jun-2009
• Referred By: ASTM D3960-05(2018) - Standard Practice for Determining Volatile Organic Compound (VOC) Content of Paints and Related Coatings
• Effective Date: 01-Jun-2009

Standards Content (Sample)

NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
Contact ASTM International (www.astm.org) for the latest information
Designation:D6886–03(Reapproved2009)
Standard Test Method for
Speciation of the Volatile Organic Compounds (VOCs) in
Low VOC Content Waterborne Air-Dry Coatings by Gas
Chromatograpy
This standard is issued under the fixed designation D6886; 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 D3792 Test Method for Water Content of Coatings by
Direct Injection Into a Gas Chromatograph
1.1 This test method is for the determination of the weight
D3925 Practice for Sampling Liquid Paints and Related
percent of individual volatile organic compounds in low VOC
Pigmented Coatings
content waterborne latex air-dry coatings. The method is
D3960 Practice for Determining Volatile Organic Com-
intendedprimarilyforanalysisofwaterbornecoatingsinwhich
pound (VOC) Content of Paints and Related Coatings
the material VOC content is below 5 weight percent. The
D4017 Test Method for Water in Paints and Paint Materials
method has been used successfully with higher VOC content
by Karl Fischer Method
waterborne coatings.
D6133 Test Method for Acetone, p-Chlorobenzotrifluoride,
1.2 This method may also be used to measure the exempt
MethylAcetateor t-ButylAcetateContentofSolventborne
volatile organic compound content (acetone, methyl acetate,
and Waterborne Paints, Coatings, Resins, and Raw Mate-
andp-chlorobezotrifluoride)ofwaterbornecoatings.Themeth-
rials by Direct Injection Into a Gas Chromatograph
odology is virtually identical to that used in Test Method
D6438 Test Method for Acetone, Methyl Acetate, and
D6133 and similar to that used in Test Method D6438.
Parachlorobenzotrifluoride Content of Paints, and Coat-
1.3 Volatile compounds that are present at the 0.05 weight
ings by Solid Phase Microextraction-Gas Chromatography
percent level or greater can be determined. Solid phase
E177 Practice for Use of the Terms Precision and Bias in
microextraction will detect volatile compounds at lower levels.
ASTM Test Methods
1.4 The values stated in SI units are to be regarded as
E691 Practice for Conducting an Interlaboratory Study to
standard. No other units of measurement are included in this
Determine the Precision of a Test Method
standard.
1.5 This standard does not purport to address all of the
3. Terminology
safety concerns, if any, associated with its use. It is the
3.1 Abbreviations:
responsibility of the user of this standard to establish appro-
3.1.1 CW/DVB—Carbowaxy/divinylbenzene
priate safety and health practices and determine the applica-
3.1.2 DB—2-(2-butoxyethoxy)ethanol; Butyl Carbitoly;
bility of regulatory limitations prior to use.
diethylene glycol monobutyl ether
2. Referenced Documents 3.1.3 EB—2-butoxyethanol; Butyl Cellosolvey; ethylene
glycol monobutyl ether
2.1 ASTM Standards:
3.1.4 EG—ethylene glycol
D1475 Test Method For Density of Liquid Coatings, Inks,
3.1.5 FID—flame ionization detector
and Related Products
3.1.6 F-VOC—formulation data calculated volatile organic
D2369 Test Method for Volatile Content of Coatings
compound in g/(L-water)
3.1.7 GC—gas chromatograph
This test method is under the jurisdiction of ASTM Committee D01 on Paint
3.1.8 PG—propylene glycol
and Related Coatings, Materials, andApplications and is the direct responsibility of
3.1.9 % RSD—percent relative standard deviation
Subcommittee D01.21 on Chemical Analysis of Paints and Paint Materials.
3.1.10 SPME—solid phase microextraction
Current edition approved June 1, 2009. Published June 2009. Originally
approved in 2003. Last previous edition approved in 2003 as D6886 - 03. DOI:
3.1.11 Std Dev—standard deviation
10.1520/D6886-03R09.
3.1.12 TX—2,2,4-trimethypentane-1,3-diol, monoisobu-
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
tyrate; Texanoly
contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM
3.1.13 VOC—volatile organic compound
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.
D6886–03 (2009)
individual volatile compound present in a coating.
3.1.14 X-VOC—experimental volatile organic compound in
g/(L-water)
5.2 SPME/GC makes it possible to identify very low levels
of volatile compounds in a coating and could serve to make it
4. Summary of Test Method
possible to identify the presence of hazardous air pollutants
4.1 A known weight of coating is dispersed in tetrahydro-
(HAPs).
furan(THF),internallystandardized,andanalyzedbycapillary
gas chromatography to give a speciated composition of the
6. Apparatus
volatile organic compounds and exempt organic compounds, if
6.1 SPME Sampling Apparatus and Fibers, manual
any, present in the coating. Summation of the individual
SPMEholdersfittedwitha70µmCarbowaxy/Divinylbenzene
volatile organic compound weight fractions gives the total
(CW/DVB) StableFlex fiber assembly.
VOC content of the coating measured in weight percent (Note
6.2 Gas Chromatograph, FID Detection with Electronic
1).
Data Acquisition System—Any capillary gas chromatograph
NOTE 1—Using the provisions of Practice D3960, the VOC content of
equipped with a flame ionization detector and temperature
coatings measured in g/Lminus water, or other units, may be determined.
programming capability may be used. Electronic flow control,
Since the determination of weight percent VOC in the present method is
which gives a constant carrier gas flow, is highly recom-
by direct measurement, either the water fraction (Test Method D3792 or
mended.
TestMethodD4017)orthenonvolatilefraction(TestMethodD2369)may
6.3 Standard FID Instrument Conditions:
be determined indirectly in the application of Practice D3960. The
equationsforcalculatingregulatoryVOCcontentwhennoexemptvolatile Detector Flame ionization
Columns Primary column: 30 m by 0.25 mm 5 % phenyl/95 % methyl
compounds are present are:
siloxane (PMPS) (Note 4),1.0µmfilmthickness.
f ~D !
VOC P Confirmatory Columns: 30 m by 0.25 mm polydimethylsiloxane
VOC 5 (1)
(PDMS), 0.25 µm film thickness; 30 m by 0.25 mm
1 2 [~1 2 f 2 f !~D /D !#
NV VOC P W
CarbowaxY (CW), 0.25 µm film thickness.
Carrier Gas Helium
or
Flow Rate 1.0 mL per min, constant flow (24.9 cm/s at 40°)
f ~D ! Split Ratio Variable
VOC P
VOC 5 (2)
Temperatures, °C
1 2 [f D /D !
~ #
W P W
Inlet 260°
Detector 270°
where:
Initial 40° for 4 min
D ,f ,f , and f = coating density, nonvolatile fraction,
P NV VOC W
Rate 10° per min to 250°, hold 5 min
VOC fraction, and water fraction, respec-
NOTE 4—The column designated as PMPS is commercially available
tively.
from several vendors by the following designations: DB-5, SPB-5, HP-5,
4.2 DirectGC/FID,GC/MSandsolidphasemicroextraction
AT-5, CP Sil 8CB, RTx-5, BP-5.
/ gas chromatography (SPME/GC) of the coating may be used
7. Reagents and Materials
to facilitate identification of the volatile compounds present in
a coating. Table X1.1 lists the GC retention times for the
7.1 Purity of Reagents—Reagent grade chemicals shall be
volatile compounds which may be found in low VOC content
used in all tests. Unless otherwise indicated, all reagents shall
waterborne air-dry coatings. Table X1.1 also lists possible
conform to the available specifications of the Committee on
internal standards for use in the analysis and minor volatile
Analytical Reagents of the American Chemical Society. Other
components which are sometimes found in waterborne coat-
grades may be used, provided it is first ascertained that the
ings (Note 2).
reagent is of sufficiently high purity to permit its use without
lessening the accuracy of the determination.
NOTE 2—The analyst should consult MSDS and product data sheets for
7.2 Carrier Gas, helium of 99.995 % or higher purity.
possible information regarding solvents which may be present in a
7.3 Tetrahydrofuran (THF), HPLC grade.
particularcoating.SPME/GCmaybeusedtoascertainthatdecomposition
volatiles are not measured.
7.4 1-Propanol, p-fluorotoluene, cyclohexanol,
p-chlorotoluene and p-cymene, 99 + mole %.
5. Significance and Use
7.5 The volatile organic compounds listed in Table X1.1.
5.1 In using Practice D3960 to measure the regulatoryVOC
7.6 Fluorocarbon-faced septum vials, 20 mL and 40 mL
content of coatings, precision tends to be poor for low VOC
capacity.
content waterborne coatings because the VOC weight fraction
is determined indirectly.The present method first identifies and
8. Column and Fiber Conditioning
then quantifies the weight fraction of individual VOCs directly
8.1 The capillary columns should be conditioned according
in low VOC content waterborne air-dry coatings. The total
to the manufacturer’s recommendation.The columns may then
VOC weight fraction can be obtained by adding the individual
be used indefinitely without further conditioning.
weight fraction values (Note 3).
8.2 TheSPMEfibershouldbeconditionedandusedaccord-
NOTE 3—An effort is currently underway in California to consider ing to the manufacturer’s recommendation.
changing mass-based VOC regulations for architectural coatings to
reactivity-based VOC regulations. In California, reactivity based regula-
tions have already been implemented for aerosol coatings, that is,
MIR-indexed regulations (California Air Resources Board). Reactivity
Available from the Supelco Company, Supelco Park, Bellefonte, PA 16823-
based regulations would require knowing the weight fractions of each 0048.
D6886–03 (2009)
8.3 The SPME fiber should be inserted into a 260°C 10.4 Chromatograph the solution in 10.3 by injecting 1 µL
injection port for 30 s prior to each sampling event. into the PMPS capillary column using the standard conditions
described in 6.3. Adjust the split ratio to give well-defined
9. Preparation of Standards chromatographic peaks. Identify the volatile compounds
present(Note7)andcalculatetheweightfractionofeachinthe
9.1 Prepare a stock mixture of ethylene glycol (EG), pro-
coating using the relationship:
pylene glycol (PG), ethylene glycol monobutyl ether (EB),
p-cymene(CY)[orothersuitableinternalstandard],diethylene AA MI 100
~ !~ !~ !
%X 5 (4)
glycol monobutyl ether (DB), and Texanol (TX) by weighing ~AI!~RF!~MC!
one or two grams of each into an appropriate vial. The weight
where:
of each component should be approximately the same and
X = one of several possible volatile compounds in the
determined to 0.1 mg. Mix the contents.
coating,
9.2 Transfer approximately 100 µLof the stock mixture to a
RF = relative response factor of compound X,
septum-capped vial containing 10 mL of THF and mix the
AA = peak area of compound X,
contents (Note 5).This solution will contain each of the known
MI = weight of internal standard in 10 mL THF,
analytes at a concentration of approximately 2 mg/mL.
AI = peak area of internal standard, and
MC = weight of coating.
NOTE 5—ThesolventsEG,PG,EB,DBandTexanolarewidelyusedin
themanufactureoflowVOCcontentwaterborneair-drycoatingsandmay
NOTE 7—If volatile compounds other than those in the standard (9.1)
be expected as highly probable components of these coatings. The
are present in the coating, the identity should be confirmed by retention
tetrahydrofuran solvent must be analyzed by GC to determine if possible
time comparison with authentic material and the relative response factor
impurities interfere/coelute with the analytes being tested.
should be determined as outlined in 9.1-9.3. Commercial Texanol may
9.3 Chromatographthesolutionin9.2byinjecting1µLinto contain small amounts of 2,2,4-trimethylpentane-1,3-diol which elutes
approximately 0.5 min before butyl carbitol. Acetone and isopropyl
the PMPS column using the chromatographic conditions given
alcohol have nearly the same retention time on a 5 % phenyl/95 % PDMS
in 6.3. Calculate the relative response factors for each of the
column and if either is found, their identities should be confirmed on a
analytes relative to the p-cymene internal standard using the
different column. Isobutyl alcohol coelutes with the solvent (THF) and
relationship:
must be determined on a different column. SPME (11.2) is especially
useful for confirming the presence of isobutyl alcohol since no THF is
AA * MI
RF 5 (3)
used in this procedure.
AI * MA
11. Solid Phase Microextraction Procedure
where:
RF = relative response factor,
11.1 Since a dispersion of coating in THF is injected into a
AA = area of analyte,
relatively hot GC injection port, peaks representing decompo-
MI = weight of internal standard (from 9.1),
sition products may be observed and should not be considered
AI = area of internal standard, and
asVOCs.Solidphasemicroextractionallowssamplingofmost
MA = weight of analyte (from 9.1).
VOCs at low temperature and may be used to determine if GC
peaks observed in the direct GC analysis (Section 10) are
10. Paint Analysis
actual VOCs or decomposition products. If desired, the SPME
10.1 Using a 100 mL volumetric flask, make up a concen-
procedure may be used prior to direct analysis to determine
trated standard solution containing p-cymene (or other suitable
which VOCs are present in the coating. If GC/MS is available,
internal standard) in THF at a concentration of approximately
the SPME procedure is especially useful for identification of
1 g per 100 mL and known to the nearest 0.1 mg.
VOCs and exempt compounds present in a coating sample.
10.2 Using standard quantitative dilution techniques, dilute
11.2 Place approximately 5 to 10 g of liquid waterborne
the concentrated standard solution to give a working standard
coating into a 40 mL fluorocarbon-faced septum vial. If using
solution such that the internal standard concentration is near 1
a smaller vial, reduce the coating amount. Close the vial with
mg per mL. Calculate the actual concentration.
a fluorocarbon-faced septum cap and heat to 55 to 60°C in an
10.3 Pipette10mLofworkingstandardsolutionintoa20or
oven or other suitable heat source (oil bath, water bath, heated
40 mL vial and close with a fluorocarbon-faced septum cap.
metal block). Do not let the contents contact the inside face of
Using a disposable 1 mLsyringe, add approximately 0.6 to 0.8
the septum cap. Insert the SPME fiber through the septum cap
g of the well-mixed paint through the septum cap and weigh to
and sample the headspace for 3 to 4 min using a conditioned
0.1 mg (Note 6). Mix the contents vigorously by shaking for 1
CW/DVB SPME fiber. Desorb the fiber for 10 s onto the
min followed by sonication for 5 min. Let the vial stand to
capillary column and obtain the gas chromatogram using the
permit pigments,
...