E PA-600/R-9 5-163
November 1995
INTERLABORATORY STUDY OF A TEST METHOD FOR
MEASURING TOTAL VOLATILE ORGANIC COMPOUND CONTENT
OF CONSUMER PRODUCTS
E. E. Rickman Jr., G. B. Howe, and R. K. M. Jayanty
P.O. Box 12194
Research Triangle Institute
Research Triangle Park, NC 27709-2194
EPA Cooperative Agreement CR-818419-02
EPA Project Officer: J. Kaye Whitfield
U.S. Environmental Protection Agency
Air Pollution Prevention and Control Division
National Risk Management Research Laboratory
Research Triangle Park, NC 27711
Prepared for:
U.S. Environmental Protection Agency
Office of Research and Development
Washington, DC 20460
-------
TECHNICAL REPORT DATA (
(Please read Instructions on the reverse before complet ||j |||| || ||||| 111 llllll III I
1. REPORT NO. 2.
EPA-600/R-95-163
3. Ill IIH II lllll Ulllllll lllll 111
PB96-121652
4. TITLE AND SUBTITLE
Interlaboratory Study of a Test Method for Measuring
Total Volatile Organic Compound Content of
Consumer Products
B. REPORT DATE
November 1995
S. PERFORMING ORGANIZATION CODE
7, AUTHOR(S)
£,E, Rickman Jr. , G. B. Howe, and R. K. M. Jayanty
8. PERFORMING ORGANIZATION REPORT NO.
RTI/5171-015-01F
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Research Triangle Institute
P. 0. Box 12194
Researxh Triangle Park, North Carolina 27709
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
CR 818419-02
12. SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
Air Pollution Prevention and Control Division
Research Triangle Park, NC 27711
13. TYPE OF REPORT AND PERIOD COVERED
Final; 5/94 - 5/95
14. SPONSORING AGENCY CODE
EPA/600/13
15.supplementary NOTES APPCD project officer is J, Kaye Whitfield, Mail Drop 61, 919/
541-2509.
is. abstract,j)e rep0rt describes results of an interlaboratory study to estimate repeat-
ability (precision of analyses performed by a single laboratory) and reproducibility
(precision analyses performed by different laboratories) of a consumer products
volatile organic compound (VOC) measurement method based on EPA Method 24 (for
VOCs in surface coatings). (NOTE; Consumer products are significant sources of
VOCs, which are precursors to the formation of ozone in photochemical smog.) The
mean method repeatability was found to be 2. 7 weight percent VOC, and the mean
method reproducibility was found to be 4i 8 weight percent VOC. Method repeatability
ranged from 0.2 to 4.4 weight percent VOC, and reproducibility ranged from 0.6 to
11.9 weight percent VOC. The precision of the consumer products VOC method for
consumer product samples is similar to that of EPA Method 24 applied to surface
coatings. Results show that the consumer products VOC method is suitable for ana-
lyzing the volatile content of a wide variety of consumer products.
17. KEY WORDS AND DOCUMENT ANALYSIS
a. DESCRIPTORS
b. 1DENTIF1ERS/OPEN ENDED TERMS
c. COS ATI Field/Group
Pollution Smog
Measurement Reproducibility
Organic Compounds _ .
Volatility
Ozone
Photochemical Reactions
Pollution Control
Stationary Sources
Consumer Products
Repeatability
13R 04B
14G
07 C
20M
07B
07E
18. DISTRIBUTION STATEMENT
Release to Public
19. SECURITY CLASS (This Report/
Unclassified
21. NO. OF PAGES
99
20. SECURITY CLASS (This page)
Unclassified
22. PRICE
EPA Form 2220-1 (9*73)
-------
NOTICE
This document has been reviewed in accordance with
U.S. Environmental Protection Agency policy and
approved for publication. Mention of trade names
or commercial products does not constitute endorse-
ment or recommendation for use.
i i
PROTECTED UNDER INTERNATIONAL COPYRIGHT
ALL RIGHTS RESERVED.
NATIONAL TECHNICAL INFORMATION SERVICE
U.S. DEPARTMENT OF COMMERCE
-------
FOREWORD
The U. S. Environmental Protection Agency is charged by Congress with pro-
tecting the Nation's land, air, and water resources. Under a mandate of national
environmental laws, the Agency strives to formulate and implement actions lead-
ing to a compatible balance between human activities and the ability of natural
systems to support and nurture life. To meet this mandate, EPA's research
program is providing data and technical support for solving environmental pro-
blems today and building a science knowledge base necessary to manage our eco-
logical resources wisely, understand how pollutants affect our health, and pre-
vent or reduce environmental risks in the future.
The National Risk Management Research Laboratory is the Agency's center for
investigation of technological and management approaches for reducing risks
from threats to human health and the environment. The focus of the Laboratory's
research program is on methods for the prevention and control of pollution to air,
land, water, and subsurface resources; protection of water quality in public water
systems; remediation of contaminated sites and groundwater; and prevention and
control of indoor air pollution. The goal of this research effort is to catalyze
development and implementation of innovative, cost-effective environmental
technologies; develop scientific and engineering information needed by EPA to
support regulatory and policy decisions; and provide technical support and infor-
mation transfer to ensure effective implementation of environmental regulations
and strategies.
This publication has been produced as part of the Laboratory's strategic long-
term research plan. It is published and made available by EPA's Office of Re-
search and Development to assist the user community and to link researchers
with their clients.
E. Timothy Oppelt, Director
National Risk Management Research Laboratory
iii
-------
ABSTRACT
Consumer products are potentially significant sources of volatile organic compounds
(VOCs), which contribute to formation of ozone in photochemical smog. Currently, the U.S.
Environmental Protection Agency (EPA) has no approved method for measuring the VOC
content of consumer products. EPA has made changes to Method 24 (for coating VOC
measurement) to adapt it to measurement of VOC in consumer products (including the contents
of aerosol cans). For its regulatory process, EPA needed information on the repeatability
(precision of analyses performed by a single laboratory) and reproducibility (precision of
analyses performed by different laboratories) of the modified method. This report describes
an interlaboratory study that was performed to obtain this information. The difference in
method precision for different products was too great to permit pooling to obtain a single
estimate of method precision. The mean method repeatability was found to be 2.7 percent,
and the mean method reproducibility was found to be 4.8 percent (both expressed as VOC
content). Method repeatabilities ranged from 0.2 to 4.4 percent, and method reproducibilities
ranged from 0.6 to 11.9 percent (both expressed as VOC content). The precision of the
modified method for consumer product samples is similar to the precision of EPA Method 24
applied to surface coatings.
iv
-------
CONTENTS
Section Page
Abstract ii
Figures iv
Tables iv
Abbreviations iv
Acknowledgments v
1. Introduction 1
2. Summary and Conclusions 3
3. Experimental Procedures 4
Method Overview 4
Preliminary Method Evaluation 5
Inter laboratory Study Design 5
Data Analysis . 9
4. Results and Discussion 14
Preliminary Method Evaluation . 14
Interlaboratory Study Data Review 15
Interlaboratory Study Results and Discussion 29
5. Quality Assurance and Quality Control 33
Overview 33
Study Protocol 33
Data Review 33
References 34
Appendixes
A. Determination of Volatile Organic Compounds in Consumer Products ... A-l
B. Laboratory Results B-l
C. Laboratory Results using Normalized IP A/IB A Ratio for Products
Containing 2-Propanol C-l
D. Interlaboratory Study Protocol D-l
v
-------
LIST OF FIGURES
Figure Page
3-1 Aerosol Sampling Adapter 6
4-la H Consistency Statistic for Total Volatile Content Measurements 21
4-lb II Consistency Statistic for Total Volatile Content Measurements 22
4-2a K Consistency Statistic for Total Volatile Content Measurements 23
4-2b K Consistency Statistic for Total Volatile Content Measurements 24
4-3a II Consistency Statistic for Water Content Measurements 25
4-3b H Consistency Statistic for Water Content Measurements ............ 26
4-4a K Consistency Statistic for Water Content Measurements ............ 27
4-4b K Consistency Statistic for Water Content Measurements . 28
TABLES
Number Page
3-1 Consumer Products Selected for Testing in Inter laboratory Study 8
3-2 Participating Laboratories 9
4-1 Results of Preliminary Product Testing . 15
4-2 Interlaboratory Study Results (Outliers Included) 17
4-3 Consistency Statistics - Total Volatile Content Measurements .......... 19
4-4 Consistency Statistics - Water Content Measurements 20
4-5 Youden Rank Sum Test for Outlying Laboratories . 30
4-6 Interlaboratory Study Results . 31
4-7 Comparison with EPA Method 24 32
LIST OF ABBREVIATIONS
ABBREVIATIONS
GC/TCD - gas chromatography with thermal conductivity detection
vi
-------
ACKNOWLEDGMENTS
This work has been supported by the U.S. Environmental Protection Agency under
EPA cooperative agreement CR-818419-02. We would also like to acknowledge the support
of the California Air Resources Board, the Bay Area Air Quality District, and the South Coast
Air Quality District, who participated without compensation as part of their continuing effort
to improve VOC measurement. We would like to thank Alberto Culver, Chesebrough Ponds,
and Gillette for supplying test samples for use in this interlaboratory study. In addition, we
would like to thank all of the participating laboratories for their time and effort.
We would especially like to recognize the contribution of EPA APPCD's J. Kaye
Whitfield to this report. Her guidance, direction, and technical assistance contributed greatly
to this work.
vii
-------
SECTION 1
INTRODUCTION
Volatile organic compounds (VOCs) are important contributors to the formation of
ozone in photochemical smog. Many consumer products contain one or more VOCs and the
use of these consumer products may be a significant source of VOCs in the environment,
EPA currently has no approved method to measure the VOC content of consumer products.
To develop such a method, work was previously performed under EPA contract to
compare two existing VOC measurement methods for their suitability for use with consumer
products. The first of these methods involved gravimetric purge and trap analysis (adapted
from California Air Resources Board Method 401), The second method, based on EPA
Reference Method 24, "Determination of Volatile Matter Content, Water Content, Density,
Volume Solids, and Weight Solids of Surface Coatings" (1), used a gravimetric determination
of total volatile content which was followed by determination of water content. The VOC
content was determined as the difference between total volatile content and water content.
Based on the results of this comparability study, a modified version of EPA Method 24 was
selected as the final test method for VOCs in consumer products. Modifications to Method
24, for analysis of consumer products, include:
• Use of a smaller sample (0.5 g versus 2 g for EPA Method 24).
• Addition of sampling procedures for products contained in pressurized (aerosol)
cans.
• Use of gas chromatography with thermal conductivity detection (GC/TCD) for
all water analysis (EPA Method 24 permits water analysis by either GC/TCD or
Karl Fischer titration).
• Use of more than one calibration point for water analysis.
• Addition of two internal standards, isobutyl alcohol (IBA) and isopropyl alcohol
(IPA) for the water analysis (only methanol is used for GC/TCD analysis in
EPA Method 24). If IPA is found in the product sample, then IB A is used as
internal standard, otherwise IPA is used. IPA is detected in the consumer
product by comparing the IPA to IB A ratio for the product (after addition of
internal standards) to the ratio for calibration standards.
For its regulatory activities, EPA needs estimates of the repeatability (precision of
analyses performed by a single laboratory) and reproducibility (precision of analyses
performed by different laboratories) for the consumer products VOC content method. This
1
-------
report describes an interlaboratory study conducted to obtain such estimates. The study design
was based on American Society for Testing and Materials (ASTM) E691-87 "Standard
Practice for Conducting an Interlaboratory Study to Determine the Precision of a Test
Method" (2). Identical samples of consumer products were sent for analyses (using the
consumer products VOC method) to a group of eight laboratories, which were selected based
on their experience and facilities. Each laboratory performed replicate analyses and reported
the results to the interlaboratory study coordinator (Research Triangle Institute fRTI]). These
results were then used to obtain estimates of repeatability and reproducibility. Estimation of
method accuracy was not possible, since the true concentrations of VOCs in the products
tested are not known.
2
-------
SECTION 2
SUMMARY AND CONCLUSIONS
Estimates of precision of the consumer products VOC method were comparable to the
precision of EPA Method 24, used for VOC measurement of surface coatings. Variation of
method precision among products was too great to permit pooling to obtain a single estimate of
method precision for all products. The estimates of repeatability ranged from 0.2 to 4.4
percent VOC with a mean of 2.7 and a median of 2.5 percent VOC. The estimates of
reproducibility ranged from 0.6 to 11.9 percent VOC with a mean of 4.8 and a median of 3.5
percent VOC.
As a result of experience gained in this interlaboratory study, two changes were made
in the proposed test method. The first was to use a normalized IP A/IB A ratio (based on peak
area per amount) to evaluate the presence of IPA in the consumer products. The effect of this
change was evaluated using the raw data from laboratories that did not appropriately detect
IPA in the samples. Using the normalized IPA/IBA ratio improved the interlaboratory study
results for products that contained IPA. The second change was to require the sampling of
pressurized (aerosol) products in the orientation normally used for dispensing the product (i.e.,
most pressurized products are sampled upright, but pressurized products normally used
inverted should also be sampled while inverted). Although this was not tested in the
laboratory, such a change should prevent sampling of headspace rather than product.
Preliminary testing showed difficulty with analysis of dense foams such as shaving
cream. No such foams were included in the interlaboratory testing and further method
development will be required for dense foams. With the exception of these foams, the VOC
method, modified as described in this report, should be suitable for determining the VOC
content of a wide variety of consumer products.
3
-------
SECTION 3
EXPERIMENTAL PROCEDURES
METHOD OVERVIEW
Previous work performed under EPA contract compared two VOC measurement
methods for use with consumer products. The first of these methods involved gravimetric
purge and trap analysis (adapted from California Air Resources Board Method 401). The
second method, based on EPA Reference Method 24 (1), used a gravimetric determination of
total volatile content which was followed by determination of water content. The VOC
content was determined as the difference between total volatile content and water content.
Based on the results of this comparability study, a version of EPA Method 24 modified for use
with consumer products (herein called the Consumer Products Method) was selected as the test
method. Changes to EPA Method 24 for use with consumer products include:
• Use of a smaller sample (0.5 g versus 2 g for EPA Method 24).
• Addition of sampling procedures for products contained in aerosol cans.
• Use of GC/TCD for all water analysis (EPA Method 24 permits water analysis
by either GC/TCD or Karl Fischer titration).
• Use of more than one calibration point for water analysis.
• Addition of two internal standards, isobutyl alcohol (IBA) and isopropyl alcohol
(IPA) for the water analysis (only methanol is used for GC/TCD analysis in
EPA Method 24). If IPA is found in the product sample, then IB A is used as
internal standard, otherwise IPA is used. IPA is detected in the consumer
product by comparing the IPA to IB A ratio for the product (after addition of
internal standards) to the ratio for calibration standards.
The Consumer Products Method (Appendix A) entails performing two separate
analyses for each product. The first analysis is to determine gravimetrically the total volatile
content of the product by evaporation in a 110° C oven for 1 hour. The measured total
volatiles include water, regulated VOCs, exempt VOCs, and inorganic volatiles (e.g., NH3).
The water content is determined using a separate sample by GC/TCD. The difference between
the total volatiles (by the gravimetric analysis) and the water content (by GC/TCD) is assumed
to be VOCs. Other volatile compounds, such as exempt VOCs and inorganic volatiles must be
determined separately (by an appropriate method) and subtracted from the VOC measured by
this method to get the actual regulated VOC content.
4
-------
PRELIMINARY METHOD EVALUATION
Several samples (one liquid, one solid, one aerosol, and three foams) were analyzed so
that RTI could become familiar with the method developed in previous work. Based on this
experience, the Consumer Products Method was revised as follows:
• The method was rewritten to improve clarity and provide a more general
method (i.e., one less specific to the equipment available in the laboratory
where the original version of the Consumer Products Method was developed),
• The first burst of product from a new can was required to be vented to clear the
eductor tube before sampling,
• The design of the aerosol/foam sampling adapter (Figure 3-1) was modified to
permit the use of "off-the-shelf" components.
The revised Consumer Products Method, as used in this interlaboratory study, is included as
Appendix A.
The design of the original sampling adapter required machining screw threads into a
commercially available pressurized (aerosol) can sampler and attaching a hypodermic needle
that had previously been silver-soldered to a matching screw-thread fitting. The apparatus
illustrated in Figure 3-1 was used in the interlaboratory study to eliminate the need for special
machining and to allow for the use of disposable needles which eliminates cleaning problems.
A sample adapter and a supply of double-ended needles were sent to the participating
laboratories with the interlaboratory study samples.
INTERLABORATORY STUDY DESIGN
The purpose of the interlaboratory study was to estimate the VOC method's precision,
both as performed in a single laboratory (repeatability) and as performed in different
laboratories (reproducibility). Guidelines for conducting an interlaboratory study provided in
ASTM E-691-87 (2) were used.
The study design called for an analysis (which is an average of two individual aliquots)
to be performed for each sample on three different days using the same analyst and equipment,
if possible. This design ensured that variations resulting from daily calibration drift, etc.,
would be included in the within-laboratory precision and the between-laboratory variation
would be influenced by differences between laboratories.
5
-------
Double-Ended Syringe Needle
Aerosol Sampling Adapter
(Alltech part no. 8048)
3
r
V
Sample Vial
Aerosol
Product
Figure 3-1. Aerosol sampling adapter.
6
-------
The study design also called for a complete VOC analysis, consisting of both total
volatile content determination and water content determination to be performed on a given
product before the analysis was repeated. This requirement ensured that the total volatile
content and water content measurements that constitute a VOC measurement would be taken
closely together. The VOC measurements would then show if any variation in product
composition (especially differing ratios of water and VOC) occurred during sampling. By
contrast, taking all three total volatile content measurements and then all three water
measurements would tend to average out the product composition and make any change less
apparent.
Selection of Consumer Product Samples
Consumer product samples were selected to provide different physical properties with a
range of water and VOC contents. Samples were categorized into four groups based on the
techniques required to obtain a sample for analysis. These categories were liquids (including
pump-type aerosol products), solids/gels, pressurized aerosols (referred to as "aerosols" -
excludes pump aerosols which are sampled as liquids), and pressurized foams (referred to as
"foams"). The samples selected for this study are listed in Table 3-1. No attempt was made
to achieve representative samples with respect to market share or usage. When selecting
products, the following issues were considered:
• Water and VOC content: A variety of products were selected to provide a
range of water and VOC contents, including products with little or no VOC
content.
• Toxicity: Highly toxic products, such as insecticides, were not selected because
of shipping, handling, and disposal problems. Other products provide similar
information on the test method without incurring the additional costs associated
with handling and disposal of toxic products,
• Availability: Liquids and granular solids were obtained in large containers to
permit splitting them into separate laboratory samples for the study. Obtaining
all of the material used in the study from a single package provided good homo-
geneity of samples and ensured that the measured interlaboratory variation did
not reflect sample variability. Separate samples (i.e., packages) of the one-
piece solid stick deodorant (which could not be easily divided) were sent to each
laboratory.
Because pressurized aerosol (and foam) cans could not be split into samples for
individual laboratories, each laboratory was sent a separate can of product. These cans were
obtained from a single lot or batch to minimize variability between samples. Whenever
possible, pressurized aerosol (and foam) samples were obtained from suppliers who would sell
products by the case. If samples were purchased off the shelf, they were matched by
production code.
7
-------
Table 3-1. Consumer Products Selected for Testing in Interlaboratory Study
Codea
Liquids (Including pump aerosols)
LA
LB
LC
LD
Solids/Gels
SA
SB
SC
SD
Aerosols (Pressurized')
AA
AB
AC
AD
Foams (Pressurized)
FA
FB
FC
FD
Product
Windshield washer fluid
Laundry prewash
Hairspray (pump aerosol)
Glass cleaner
Stick deodorant (one-piece solid)
Tile cleanser (granular solid)
Cold cream (gel)
Laundry detergent (granular solid)
Furniture cleaner/wax
Hairspray
Deodorant
Glass cleaner
Carpet cleaner
Tire cleaner
Household cleaner
Engine cleaner
a Categories are based on the sampling technique required for analysis.
Sample codes were randomly assigned to products within each
category.
All samples were divided and assigned in random order to the laboratories before the
study began. The laboratories were sent a package containing all of the samples, the aerosol
sampling adapter, double-ended syringe needles, a short piece of vinyl tubing (used to adapt
the sampling adapter to small diameter aerosol valve stems), and study protocol. The samples
were not refrigerated in storage but were kept at normal room temperatures.
Selection of Participating Laboratories
Participating laboratories were selected by calling a group of environmental
laboratories to assess their willingness to participate. Those interested were sent a copy of a
draft laboratory protocol, including a draft version of the Consumer Product Method, and
were requested to submit a proposal (which included pricing for commercial laboratories).
8
-------
Three California state laboratories (California Air Resources Board, Bay Area Air Quality
Management District, and South Coast Air Quality Management District) agreed to participate
without financial reimbursement. Four additional commercial laboratories were then selected.
RTI also participated as one laboratory in the interlaboratory study. Code letters A, B, D, E,
F, G, H, and J were randomly assigned to the participating laboratories for identification. The
participating laboratories are listed in alphabetical order (i.e., not by code letter) in Table 3-2.
Although the code letter used by each laboratory is not revealed in this report, the same code
letter was used to refer to a given laboratory throughout the study and this report.
Table 3-2. Participating Laboratories
Name8
Location
Applied P&Ch Laboratory
Atmospheric Analysis and Consulting
Bay Area Air Quality District
California Air Resources Board
Midwest Research Institute
Research Triangle Institute
Smith Emery Company, Inc.
Southcoast Air Quality District
Pomona, CA
Ventura, CA
San Francisco, CA
Sacramento, CA
Kansas City, MO
Research Triangle Park, NC
Los Angeles, CA
Diamond Bar, CA
a Laboratories are in alphabetical order in this table - laboratory codes were
randomly assigned and are not in this order.
DATA ANALYSIS
Calculations for the total volatile content determination, the water content
determination, and the volatile organic content determination were performed as described in
the Consumer Products Method (Appendix A). Precision estimates (repeatability and
reproducibility) were calculated separately for the total volatile content determination, the
water content determination, and for the VOC content determination.
Repeatability
The repeatability (sr), or within-laboratory precision, was calculated separately for each
product and type of determination (i.e., total volatile, water, and VOC), as described in
ASTM E-691 87 (2), The average value for each laboratory (x) was calculated as:
9
-------
n
£ *,
(i)
x
n
where
Xj = i- measurement
n = number of measurements
The single laboratory standard deviation (s) was calculated for each laboratory as:
£ (x, - ip
1 = 1
(2)
s = *
\ ("-1)
where
x. = laboratory value for measurement
x = average value for laboratory (equation 1)
n = number of measurements made by that laboratory.
The repeatability (sr) was then calculated as the square root of the average within-
laboratory variance (with each laboratory weighted equally) or:
Sj - standard deviation of measurements for laboratory i (Equation 2)
p = number of laboratories.
Reproducibility
The reproducibility (sR), which includes within-laboratory and between-laboratory
precision, was calculated separately for each product and type of determination (i.e., total
volatile, water, and VOC), as described in ASTM E-691 87 (2). First, the average value for
all laboratories (x) (all laboratories weighted equally) was calculated as:
(3)
where
10
-------
where
Xj = average value for laboratory j (Equation 1)
p = number of laboratories.
Then, the standard deviation of laboratory averages (s_) was calculated as:
t fc -*)!
„ - i=j
where
Xj = average value for ja laboratory (Equation 1),
x = average value for all laboratories (Equation 4), and
p = number of laboratories.
The reproducibility (sR) is then calculated as:
Sr
2 Sr (n " 1)
s- +
n
if (sR > sr) or,
SR = Sr
where
s- = standard deviation of laboratory averages (Equation 5),
sf = repeatability (Equation 3), and
n = number of replicate analyses performed by each laboratory.
Consistency Statistics
Potential outliers in the interlaboratory data set were identified by calculating
laboratory consistency statistics as described in ASTM E 691-87 (2),
11
-------
Laboratory Mean Consistency Statistic, The laboratory mean consistency statistic (h) is
calculated, for each laboratory, as:
b = i-li (7)
where
s- = standard deviation of laboratory averages (Equation 5)
x = average of values for this laboratory (Equation 1)
x = average of values for all laboratories (Equation 4)
This may be compared to the critical value of h Ow), which may be obtained from
tables in ASTM E 691-87 (2) or calculated as:
hcrit - (p " 1 )tv'p(t2 + P 2) (8)
where
p = number of laboratories
t = Student's t statistic for 0.5 percent (i.e., 0,005 confidence, two-sided)
with p - 2 degrees of freedom.
A value of h greater whose absolute value is greater than htrit suggests that one or more of the
laboratory's analyses are outliers and should be removed from the data set.
Laboratory Variance Consistency Statistic. The laboratory variance consistency statistic (k)
is calculated for each laboratory as:
k =
r <»>
where
s = standard deviation of values in laboratory (Equation 2)
s = repeatability (Equation 3).
12
-------
This may be compared to the critical value of k (km[), which may be obtained from
tables in ASTM E 691-87 or calculated as:
P
7~7 do)
where
p = number of laboratories
F = Value of Fisher's F distribution with 0.005 confidence and (n -1) and (p -1)
(n - 1) degrees of freedom, where n is the number of samples analyzed
by each laboratory.
A value of k greater than k^ suggests that one or more analyses are outliers and should be
removed from the data set.
Youden's Test for Outlying Laboratories
Youden's test for outlying laboratories (3,4) was used to examine whether any
laboratory obtained values consistently higher or lower than the other laboratories. This test
involves ranking the laboratory results for each sample. The ranks of each laboratory are then
totaled over all samples (with results reported by all laboratories) to give a rank sum for each
laboratory. Rank sums exceeding critical values given in reference tables (3,4) indicate that
the laboratory's results may be systematically different from other participating laboratories.
13
-------
SECTION 4
RESULTS AND DISCUSSION
The results and discussion are divided into three sections. The first section discusses
the preliminary method evaluation. The second section discusses the review of the
interlaboratory study data to identify and remove outliers. The third section discusses the
results of the interlaboratory study.
PRELIMINARY METHOD EVALUATION
Several preliminary product samples (one liquid, one solid, one aerosol, and several
foams) were analyzed to allow RTI to become familiar with the Consumer Products Method as
developed in earlier work. Results are presented in Table 4-1. Two of the same products
were also used in the interlaboratory study (different production lots were used in the
interlaboratory study samples). In general, method precision for both solid and liquid samples
was good.
Problems were experienced with the first pressurized foam sample (shaving cream).
This sample produced an extremely thick foam that did not dissolve in the dimethylformamide
(DMF), used as a solvent for the water analysis. The mixture that resulted after addition of
DMF was too viscous to pass through a syringe for injection into the gas chromatograph. No
water analysis (and thus no VOC determination) could be performed with this sample. Two
other samples (a pressurized aerosol window cleaner that produces a light foam when sprayed
and a pressurized foam engine cleaner) dissolved well in DMF and thus could be analyzed.
Modifications to the method that would permit analysis of dense foams were considered to be
too extensive for the current study. Due to the problems with dense foams, no such samples
were included as part of the interlaboratory study. Future work still needs to be done to
accommodate these products by the method.
The results of the first water analysis aliquot for the window cleaner were much lower
than results for subsequent aliquots (61 percent water for the first aliquot versus an average of
93 percent water for the next five aliquots). The low water results are believed to be due to
the first aliquot having been taken from an unused can. Pressurized aerosol cans contain an
eductor tube that may be filled with propellant initially. The first venting from such a can
would contain largely propellant (and thus little water). The high level of propellant in the
first aliquot was verified by calculating the percentage of propellant (with respect to total
sample weight) for all aliquots. The first aliquot had 25 percent propellant while the other five
aliquots ranged from 0.8 to 3.2 percent propellant. To prevent a similar problem in future
work, the Consumer Products Method was modified to require discarding a short burst (thus
14
-------
filling the eductor tube with product) before sampling from a new can. Other minor changes
to the method were also made as a result of experience gained performing the preliminary
study (these are discussed in Section 3, Experimental Procedures).
Table 4-1, Results of Preliminary Product Testing
Percent volatile content by weight
Total (std dev)a Water (std dev)a Volatile organic
Windshield washer fluid
100.0 (0.0)
67.7 (0.8)
32.3
Stick deodorantb
59.3 (1.5)
1.7 (0.1)
57.7
Aerosol deodorantb
63.8(3.1)
2.1 (0.2)
61.7
Shaving foam
93.4 (5.1)
NAC
NA
Window cleaner0
99.7 (0.5)
80.6 (2,5)e
19.1
Engine cleaned
93.7 (0.5)
66.7 (5.4)
26.9
2 Average of six replicate analyses, value in parentheses is the standard deviation.
b Not same product as used in interlaboratory study.
c NA = Not available, sample remained as a dense foam and could not be injected
into GC for water analysis.
d Not same lot as used in interlaboratory study.
c Based on five replicate analyses. First aliquot drawn from new can had very high propellant ratio (and
thus low water content by weight).
INTERLABORATORY STUDY DATA REVIEW
For quality assurance purposes, the data received from the participating laboratories
were reviewed before assessing the overall method performance. Data received from the
laboratories were entered into computer spreadsheets for calculations of repeatability and
reproducibility for each product. Results from the participating laboratories are summarized
by product in Appendix B. The entries were checked against the original data sheets (as
received from the participating laboratories); however, no attempt was made to verify the
calculations for each laboratory. Major errors in calculations would be detected by outlier
tests, described below. Items addressed in the data review include: missing and truncated
data, sampling of inverted aerosol cans, detection of IPA in products, and detection and
treatment of outlying data (either by sample or by laboratory).
Missing and Truncated Data
Some laboratories forced negative values to zero or reported values greater than
100 percent as 100 percent. Where this truncation was detected, corrected values were
calculated from the original laboratory data sheets and used for all calculations.
15
-------
One laboratory (Laboratory G) did not detect any water in three of the solid samples
(SA, SB, and SD) and reported a value of zero for all three samples on all three days. These
values were not used, since they have artificially good precision. A second laboratory
(Laboratory H) performed an initial analysis on these same samples and noticed that the water
level was below their established detection limits. No further water analyses were then
performed on these samples by this laboratory.
Sampling of Inverted Products
The repeatability and reproducibility data collected before removal of outliers are given
in Table 4-2. Product FA (carpet cleaner) had noticeably poorer precision for the water
analysis than the other products. This was the only product tested that specified use with the
can inverted. Because the product is used in an inverted position, the eductor tube extends
only partially into the can (this was verified by venting and opening a sample can). Samples
taken with the can in an upright position would sample headspace rather than product and
would have varying amounts of water depending on the amount of liquid bubbles (produced by
shaking the can) present in the headspace. This variability would account for the poor water
content precision seen by the participating laboratories. Since both water and propellant are
volatile compounds, various mixtures of water and propellant still produce high total volatiles
and the total volatile content precision appears good. As a result of experience with this
product, the method was modified to include a statement that products should be sampled in
the orientation specified for normal use (i.e., products with instructions that specify upright
use should be sampled upright, products that specify inverted use should be sampled with the
product inverted). The results for product FA were considered not representative of the
method performance and were removed from the final data set. After removal of product FA,
there were no results from inverted products in this study.
Detection of IPA
The Consumer Products Method was improved with respect to EPA Method 24 by
including a mechanism to detect the presence of the new internal standard, IPA, as a product
component. Two study products, the glass cleaner samples (liquid product LD and aerosol
product AD), contained IPA. An important test of the method is to see whether the
laboratories detected IPA in these products. As shown in Appendix B, most, but not all
laboratories detected IPA and used IBA as the internal standard. The inability of some
laboratories to detect IPA in these products was due to difficulties in precisely delivering the
small quantity (0.2 g) of IPA and IBA as internal standards. The confidence limits for
detection of IPA include both variation in detector response as well as variation in the amount
of each internal standard (IPA and IBA) added to each sample. Since the actual amount of
16
-------
Table 4-2, Intel-laboratory Study Results (Outliers Included)
Product
Total volatiles {
Water content (%)
VOC (%)
No. of
labs Avg.
Repeat-
ability
Reproduc-
ibility
No. of
labs Avg.
Repeat-
ability
Reproduc-
ibility
No. of
labs Avg.
Repeat-
ability
Reproduc-
ibility
LA - Windshield washer fluid
8
99.98
0.03
0.04
8
70.39
1.04
11.92
8
29.58
1.05
11.93
LB - Laundry prewash
8
90.12
0.07
0.09
8
89.45
3.13
3.34
8
0.71
3.16
3.37
LC - Hairspray (pump type)
8
94.20
0.07
0.21
8
14.55
3.34
3.34
8
79.65
3.32
3.34
LD - Liquid glass cleaner5
8
99.85
0.04
0.04
8
88.44
3.24
6.42
8
11.41
3.22
6.42
SA - Stick deodorant
8
53.01
0.55
2.25
6
1.16
0.57
1.22
6
51.85
0.96
3.50
SB - Tile cleaner
8
0.69
0.12
0.20
6
0.51
0.16
0.47
6
0.15
0.23
0.63
SC - Cold cream
8
38.46
1.76
5.31
8
30.43
3.40
5.16
8
8.03
4.14
7.21
SD - Laundry detergent
8
1.69
0.33
0.86
6
1.97
0.23
0.71
6
-0.44
0.39
1.36
AA - Furniture polish
8
94.27
1.05
4.32
8
72.64
4.61
5.06
8
21.62
4.19
4.65
AB - Aerosol hairspray
8
95.57
0.36
0.76
8
17.77
1.73
3.72
8
78.03
2.51
4,14
AC - Aerosol deodorant
8
99.88
0.14
0.38
8
5.99
0.31
0.68
8
93.80
0.38
0.81
AD - Glass cleaner*
8
99.61
0.18
0.25
8
91.52
4.80
7.23
8
8,40
4.02
7.14
FA - Carpet cleaner4
8
98.35
0,50
0.88
8
61.68
8.08
22.77
8
36,71
8.20
23,33
FB - Tire cleaner®
8
68.67
3.68
10.76
8
62.91
1.87
2.52
8
5.76
3.97
10.18
FC - Wall cleaner
8
97.89
0.17
0.49
8
92.67
1.79
3.31
8
5.23
1.78
3.58
FD - Engine cleaner
8
93.41
0.40
0.59
8
70.50
3.32
3.32
8
22.93
3.48
3.48
1 Some laboratories did not delect isopropyl alcohol in these products.
b Samples should have been taken with product inverted. These data have been removed from final data set.
c One laboratory had problems with incomplete evaporation.
-------
each internal standard is weighed as part of the method, it is possible to modify the
calculations to adjust for the mass variations by using the normalized IPA/IBA ratio defined
as:
{ IPA area ^
mA , m. .. v IPA mass,
IPA to IB A ratio =
IBA area
IB A mass
A confidence interval is then defined (as before) as three standard deviations of the
normalized ratio for the calibration standards. Calculations were repeated (using the
normalized ratio) for the laboratories that did not consistently detect IPA in the product and
the results are given in Appendix C. The use of the normalized ratio greatly improved the
ability of laboratories to detect the presence of IPA in the glass cleaners. This suggests that
the method should be modified to include the use of the normalized IPA/IBA ratio. The final
data set included the glass cleaner results in Appendix € (i.e., using the normalized IPA/IBA
ratio).
Detection and Treatment of Outliers
The laboratory data were reviewed for potential outliers using the consistency statistics
described in ASTM E 691 (2). In addition, Youden's Test for Outlying Laboratories (3,4)
was used to evaluate whether a given laboratory's results were consistently greater or lesser
than other laboratories.
Review of Consistency Statistics. ASTM E 691 describes two consistency statistics for use in
examining the study data for possible outliers. The h statistic reflects a laboratory's deviation
from the mean value of the other laboratories while the k statistic reflects the variance of the
laboratory relative to the other laboratories. The consistency statistics for the preliminary data
set (with the removal of product FA and the use of the modified IPA/IBA ratio) are given in
Tables 4-3 and 4-4 and are shown in Figures 4-1 through 4-4. The critical values for these
statistics (at 99.5 percent) are also given in Tables 4-3 and 4-4.
The data flagged by the consistency statistics were reviewed to find potential causes
that might lead them to be classified as outliers. A possible cause was found for the total
volatile content values for product FB Tire Cleaner analyzed by Laboratory E. These values
had both poor precision (standard deviation of 9.6 percent total volatiles) and poor accuracy (-
24.4 percent difference from the grand mean). All three Laboratory E total volatile content
measurements for this product were lower than the measurements reported by any other
laboratory. The most likely reason for this was slow evaporation of water from the opened
serum bottle in the oven. Although a mechanically stirred convection oven was specified in
18
-------
Table 4-3. Consistency Statistics - Total Volatile Content Measurements
Lab
A
B
D
E
F
G
H
I
LA - Windshield Washer Fluid
h
-0.11
0.58
-2.20
0.81
0.23
0.22
0,93
-0.46
{critical h = 2.15, k = 2.06)
k
0.21
0.86
1.22
0,00
1.07
2.10
0,43
0.14
LB - Laundry Prewasn
h
-1.80
0.11
-0.81
-0,29
-0,07
0.55
1,05
1.27
(critical h = 2.15, k = 2,06)
k
2.34
0.66
0.60
0.25
0,30
0.78
0.50
0.83
LC - Hairspray (pump type)
h
1,89
-0.26
0.12
0.53
-0.97
-0.26
0.35
-1.39
(critical h = 2,15, k = 2.06}
k
0.24
0,32
0.75
1.14
0.91
1.45
0.87
1.51
LD - Liauid Glass Cleaner
h
-0.94
0.29
-1,28
0.15
0.97
1.08
0.92
-1.18
(critical h = 2.15, k = 2.06)
k
0.44
1.15
1.45
0.59
1.19
0,72
1.23
0.76
SA - Stick Deodorant
h
1.52
-0.66
0.18
-1.29
-0.97
-0.17
0.16
1.25
(critical h = 2.15, k = 2.06)
k
1.31
1.05
1.47
0.34
1.01
0.33
0.48
1.23
SB - Tile Cleaner
h
0.76
0.00
0.58
2.22
-0.30
0.06
1.02
0.11
(critical h = 2.15, k = 2.06)
k
0.32
0.89
0.14
0.61
1.59
1.57
0.34
1.27
SC - Cold Cream
h
0.49
-0.83
1.02
-0.53
-1.59
-0.14
0.10
1.47
(critical h = 2.15, k = 2.06)
k
0.80
0.45
0.84
0.33
1.42
1.93
0.15
0.78
SD - Laundrv Deteraent
h
1.75
-0.18
-0.46
-1,43
-0,79
0.17
0.99
-0.05
(critical h = 2.15, k - 2,06)
k
0.62
0,82
0.33
0.18
0.61
0.94
0.90
2.17
AA - Furniture Polish
h
0.34
0.35
0.31
2.46
0.28
0.61
0.31
0.26
(critical h = 2,15, k = 2.06)
k
0.09
0.68
0.19
0.47
2,25
0.66
0.16
1.32
AB - Aerosol Hairsorav
h
0.89
0.33
-1,72
0.04
-1.32
1.04
0.50
0.23
(critical h = 2.15, k = 2,06)
k
0.29
0.30
0.97
0,99
1,00
1.58
1.36
0.73
AC - Aerosol Deodorant
h
0.12
-0.85
-0.14
-0,91
-0,30
2.30
-0.21
-0.01
(critical h = 2.15, k = 2,06)
k
0.28
0.69
0.69
1.29
1.40
0.30
0,57
1.71
AD - Glass Cleaner
h
-0.53
-1.18
-0.36
-0.61
-0.07
1.54
-0.31
1.53
(critical h = 2.15, k = 2.06)
k
0,09
0.74
0.28
0,28
1.20
0.43
1.28
2.01
FB - Tire Cleaner
h
0.79
0.05
0.65
-2.36
-0.14
0.24
0.42
0.35
(critical h = 2.15, k = 2.06)
k
0.06
0.73
0.07
2.61
0.44
0.33
0.08
0.60
FC - Wall Cleaner
h
0,60
-0.81
-0.26
-0,52
-0.26
2,24
-0.35
-0.85
(critical h = 2.15, k = 2,06)
k
0.91
0.82
0.34
0.26
0.64
1.58
1,80
0.40
FD - Enaine Cleaner
h
1.43
-1.02
-0.18
-0.27
-1.16
1.51
-0,43
0.11
(critical h = 2.15, k = 2.06)
k
0.15
0.84
0.58
0.67
2.14
0.82
0.35
1.05
a Exceeds critical value.
-------
Table 4-4. Consistency Statistics - Water Content Measurements
Laboratory
A
B
D
E
F
G
H
J
LA - Windshield Washer Fluid
h
2,10
0.05
0.10
-0.41
-0.17
-1.53
-0.19
0.04
{critical h = 2.15, k = 2.06}
k
0.46
1.08
2.19
0.53
0.64
0.44
0.52
0.82
LB - Laundrv Prewash
h
-0.17
0.83
-1.04
1,73
0.30
-1.40
0.13
-0.38
{critical h = 2.15, k = 2.06}
k
0.04
0.13
2.40
1.26
0.36
0.16
0.10
0.68
LC - Hairsorav loumD tvoe)
h
-0.58
0.96
-0.64
-0.52
2.08
-0.77
-0.25
-0.27
{critical h = 2.15, k = 2.06}
k
0.10
0.30
0.13
0.20
2.80
0.09
0.02
0.03
LD - Liquid Glass Cleaner®
h
-0,70
0.94
-0.10
0.32
0.82
-0.60
1.12
-1.79
{critical h = 2.15, k = 2.06)
k
0,02
0.11
1.75
1.56
1,03
0.54
0.73
0.79
SA - Stick Deodorant
h
-1,03
1,86
-0.46
0.17
-0.08
ND
NDC
-0.46
{critical h = 1.92, k = 1.98)
k
0.66
2.081
0.75
0,68
0.16
ND
NDC
0.45
SB - Tile Cleaner
h
-1.27
1,14
-0.69
1.14
-0,53
ND
NDC
0.20
(critical h = 1,92, k = 1.98)
k
1.41
0.94
0.49
1.32
0,55
ND
NDC
0.92
SC - Cold Cream
h
0.55
0.98
0.25
0.44
1.87
0.21
0.65
-1.22
{critical h = 2.15, k = 2.06}
k
0.74
0,21
0.35
1.29
2.28
0.52
0.11
0.36
SD - Laundry Deteraent
h
-1,00
1.40
-0,46
0.89
-0,99
ND
NDr
0.16
{critical h = 1.92, k = 1.98)
k
0,32
1.17
0,40
1.54
1.00
ND
NDC
0.99
AA - Furniture Polish
h
-0.52
1.06
1,39
-1.70
0,47
-0.04
0.08
-0.74
{critical h = 2.15, k = 2.06)
k
0,54
0.82
0.74
0.07
2.20
1.09
0,30
0.82
AB - Aerosol Hairsprav
h
-0,08
-0.22
1.60
1.12
0.36
-1.42
-0.48
-0.88
{critical h = 2.15, k = 2.06}
k
0.19
0.09
1.59
0.55
0,77
0.58
0.38
2.01
AC - Aerosol Deodorant
h
-0.52
0.98
0.81
1.54
-1,34
0.29
-0.87
-0.31
{critical h = 2.15, k = 2.06)
k
0.28
0.70
1.05
1.40
1.32
1.42
0.25
0.73
AD - Glass Cleanerb
h
-0.27
-0.89
0,92
1.85
0.08
-0.44
0.03
-1.29
{critical h = 2.15, k = 2.06}
k
0,35
1.62
0.51
0.85
0.14
1.54
1.16
0.72
FB - Tire Cleaner
h
-0.58
-0,37
1.35
-0.95
-0.36
1.14
0.97
-1.20
(critical h = 2.15, k = 2.06}
k
0.47
0.51
0.45
1.13
2.131
1.00
0.35
0.60
FC - Wall Cleaner
h
-1.23
0.70
0.36
1.27
0.57
-0.89
-1.34
0,57
(critical h = 2.15, k = 2.06)
k
2,31
0.35
0.23
0.60
1.01
0.37
0,81
0.58
FD - Erics ine Cleaner
h
-0.02
0,52
1.07
-1.01
-0.77
0.17
1.42
-1.39
(critical h = 2.15, k = 2.06)
k
0.38
0.14
2,43
0.30
0.52
0.62
0.26
1.05
Exceeds critical value, b Product contains 1PA. Calculations modified to use normalized I PA/IB A ratio.
ND = One or more laboratories did not detect water in this product.
-------
3
2
1
o
T3
*W 0
~w
-1
-2
-3
LA LB LC LD SA SB SC SD
product
Laboratory
H & :IZ d ^ E ¦ F ^2 G 5Sh ¦ J
Figure 4-la. H consistency statistic for total volatile content measurements
-------
3
.o
.*2
5
W
0
W
M
to
£
_
£
Ql
Oi
at
t/i
a
-<4—1
O
z
AA AB AC AD FA
product
Laboratory
77\ e ¦ F
A H B i : D V"
Figure 4-1 b. II consistency statistic for total volatile content measurements
FB
FC
FD
H
-------
3
2.5
2
tn
LA LB LC LD SA SB SC SD
product
Laboratory
i A ¦ & ^ E ¦ F J G S" H-J
Figure 4-2a. K consistency statistic for total volatile content measurements
-------
3
2.5
.a
UB
5
w
'¦S 1.5
0.5
w
E
jd
_£1
o
«_
CL
TO
E
m
40
a
4)
¦a
jj
_Q
J5
<0
>
ffl
AA AB AC AD FA
product
Laboratory
EH* ¦ B Hd ^ E ¦ F
Figure 4-2b. K consistency statistic for total volatile content measurements
FB
FC
5^ H
FD
-------
3
<-h
tn
s 0
«3»
-1
-2
-3
LA
LB
LC LD SA
product
Laboratory
E ¦ F
SB
SC
SD
= A ¦ B D
Figure 4-3a. H consistency statistic for water content measurements
H
-------
3
.52
<3
to
w
-2
-3
w
a»
en
21
Figure 4-3b. H consistency statistic for water content measurements
FB
FC
FD
H
-------
LC
LD SA
product
Laboratory
E ¦ F
SB
SC
SD
EEJ A ¦ B I ! D
Figure 4-4a. K consistency statistic for water content measurements
52 h
-------
3
AA
\
\
} \
I i
s s
i 3
AB
m
E
jj
_Q
O
a.
C8
c
"5.
E
(TJ
05
Q
-------
the method, Laboratory E used a thermal convection (i.e., no fan) oven. Previous experience
at RTI has shown that thermal convection ovens may not provide adequate air movement to
remove water from the narrow top serum bottle. Such problems may depend on bottle
placement in the oven and not be easily reproduced. Based on our experience, it appears that
the Laboratory E total volatile content data for product FB that were flagged by the
consistency statistics represent outliers and have been removed from the final data set. No
reason could be found to designate any other flagged data as outliers and all other flagged data
were used.
Review of Laboratory Rank Sums. Youden's test for outlying laboratories (3,4) was also
applied to examine whether any laboratory obtained values consistently higher or lower than
the other laboratories. Only products that included results from all laboratories were included.
Product FA (carpet Cleaner) was not included due to sampling problems. The results are
shown in Table 4-5. Critical rank values were obtained from reference tables (3,4) for
95 percent confidence. No laboratory exceeded the upper or lower rank sum for any type of
determination (total volatiles, water content, or VOC). Thus, no consistent difference between
laboratories was demonstrated.
INTERLABORATORY STUDY RESULTS AND DISCUSSION
The interlaboratory study results are presented in Table 4-6. Bartlett's test for
inhomogeneity of variances (5) was applied across products to the repeatability and
reproducibility estimates for each determination, with the result that none of the precision data
were sufficiently homogeneous to pool for a single number for each method (i.e., total
volatile, water content, or VOC). Linear regressions were attempted for precision versus the
reported value of each determination; however, only the repeatability versus water content
regression showed a statistically significant slope. Thus, in general, there was no reasonable
way to combine the data in Table 4-6 to obtain a single pooled estimate of method precision.
This is not surprising considering the wide variation in the products tested (i.e. the method
precision varies with product composition sufficiently to prevent a single estimate of method
precision from the products tested).
Although a single estimate of method precision could not be obtained, it is interesting
to compare the mean and median precision estimates to those of EPA Method 24 (2) for
surface coatings (Table 4-7). EPA Method 24 reports the estimate of the method's relative
standard deviation (implying that the repeatability and reproducibility values increase with total
volatile and water content). Because no such dependency was demonstrated in our study data,
the absolute standard deviation was reported for the Consumer Products Method. For
products with high total volatiles or water content, the relative standard deviation and absolute
standard deviation are approximately the same. The precision of the consumer product method
is consistent with that of EPA Method 24 for surface coatings, especially
29
-------
Table 4-5. Youden Rank Sum Test for Outlying Laboratories
Laboratory Rank
A B D E F G H J
Total volatiles1
LA - Windshield washer fluid
3
6
1
7
5
4
8
2
LB - Laundry prewash
1
5
2
3
4
6
7
8
LC - Hairspray (pump type)
8
3
5
7
2
4
6
1
LD - Liquid glass cleaner
3
5
1
4
8
6
7
2
SA - Stick deodorant
8
3
6
1
2
4
5
7
SB - Tile cleaner
7
3
6
1
2
4
8
5
SC - Cold cream
6
2
7
3
1
4
5
8
SD - Laundry detergent
8
4
3
1
2
6
7
5
AA - Furniture polish
6
7
5
1
3
8
4
2
AB - Aerosol hairspray
7
5
1
3
2
8
6
4
AC - Aerosol deodorant
7
2
5
1
3
8
4
6
AD - Glass cleaner
3
1
4
2
6
8
5
7
FC - Wall cleaner
7
2
6
3
5
8
4
1
FD - Engine cleaner
7
2
5
4
1
8
3
6
Total (Critical sums < 39 or > 87)
81
50
57
41
46
86
79
64
Water Content8
LA - Windshield washer fluid
8
6
7
2
4
1
3
5
LB - Laundry prewash
4
7
2
8
6
1
5
3
LC - Hairspray (pump type)
3
7
2
4
8
1
6
5
LD - Liquid glass cleaner"
2
7
4
5
6
3
8
1
SC - Cold cream
6
8
4
5
1
3
7
2
AA - Furniture polish
3
7
8
1
6
4
5
2
AB - Aerosol hairspray
5
4
8
7
6
1
3
2
AC - Aerosol deodorant
3
7
6
8
1
5
2
4
AD - Glass cleaner"
4
2
7
8
6
3
5
1
FB - Tire cleaner
3
4
8
2
5
7
6
1
FC - Wall cleaner
2
7
4
8
6
3
1
5
FD - Engine cleaner
4
6
1
2
3
5
8
1
Total (Critical sums < 32 or > 76)
47
72
67
60
58
37
59
32
VOC Results®
LA - Windshield washer fluid
1
3
2
7
5
8
6
4
LB - Laundry prewash
5
2
7
1
3
8
4
6
LC - Hairspray (pump type)
8
2
6
5
1
7
4
3
LD - Liquid glass cleaner"
7
2
5
4
3
6
1
8
SC - Cold cream
6
1
7
2
5
4
3
8
AA - Furniture polish
7
3
2
1
4
6
5
8
AB - Aerosol hairspray
4
5
1
2
3
8
6
7
AC - Aerosol deodorant
6
2
3
1
8
5
7
4
AD - Glass cleaner"
4
7
2
1
3
5
6
8
FC - Wall cleaner
8
2
5
1
4
6
7
3
FD - Engine cleaner
5
3
2
7
4
6
1
8
Total (Critical sums < 29 or > 70)
61
32
42
32
43
69
50
67
1 Ranking was performed only for products with all laboratories reporting results. Product FA (carpet
cleaner) was not included due to sampling problems,
h Calculations modified to use normalized IPA/IBA ratio
30
4
-------
Table 4-6, Interlaboratory Study Results8
Total volatiles {%)
Water content (%)
VOC<%)
No. of
Repeat- Reproduc-
No. of
Repeat-
Reproduc-
No. of
Repeat-
Reproduc-
Product
labs
Avg.
abilitv
ibility
labs
Avg.
ability
ibility
labs
Avg.
ability
ibility
LA - Windshield washer fluid
8
99.98
0.03
0.04
8
70.39
1.04
11.92
8
29.58
1.05
11.93
LB - Laundry prewash
8
90.12
0.07
0.09
8
89.45
3.13
3.34
8
0.71
3.16
3.37
LC - Hairspray (pump type)
8
94.20
0.07
0.21
8
14.55
3.34
3.34
8
79.65
3.32
3.34
LD - Liquid glass cleaner"
8
99.85
0.04
0.04
8
92.10
1.33
1.75
8
7.75
1.32
1.73
SA - Stick deodorant
8
53.01
0.55
2.25
6
1.16
0.57
1.22
6
51.85
0.96
3.50
SB - Tile cleaner
8
0.69
0,12
0.20
6
0.51
0.16
0.47
6
0.15
0.23
0.63-
SC - Cold cream
8
38.46
1.76
5.31
8
30.43
3.40
5.16
8
8.03
4.14
7.21
SD - Laundry detergent
8
1.69
0.33
0.86
6
1.97
0.23
0.71
6
-0.44
0.39
1.36
A A - Furniture polish
8
94.27
1.05
4.32
8
72.64
4.61
5.06
8
21.62
4.19
4.65
AB - Aerosol hairspray
8
95.57
0.36
0.76
8
17.77
1.73
3.72
8
78.03
2.51
4.14
AC - Aerosol deodorant
8
99.88
0.14
0.38
8
5.99
0.31
0.68
8
93.80
0,38
0.81
AD - Glass cleaner15
8
99.61
0.18
0.25
8
93.61
4.83
5.54
8
6.32
4.41
5.43
FA - Carpet cleaner®
FB - Tire cleaner
7
72.15
1.53
3.59
8
62.91
1.87
2.52
7
8.97
2.59
4.14
FC - Wall cleaner
8
97,89
0.17
0.49
8
92.67
2.79
3.31
8
5.23
1.78
3.58
FD - Engine cleaner
8
93.41
0.40
0.59
8
70.50
3.32
3.32
8
22,93
3.48
3.48
Mean4
75.39
0.70
2.11
47.78
2.60
4.44
27.61
2.68
4.80
Median
94.20
0.18
0.49
62.91
1,79
3.32
8.97
2.51
3.50
Max
99.98
1.76
5.31
93.61
4.83
11.92
93.80
4.41
11.93
Min
0.69
0.03
0.04
0.51
0.16
0.47
-0.44
0.23
0.63
1 Outliers have been removed.
1 Product contains IPA. Calculations modified to use normalized IPA/IBA ratio.
e Not Included due to sampling problems.
" Mean repeatability and reproducibility are square root of mean variance with all products weighted equally.
-------
Table 4-7. Comparison with EPA Method 24
Consumer Products Method
standard deviation*
Meanb Median
EPA Method 24
Relative standard deviation0
Total volatiles (%)
ASTM D2369
Repeatability
0.70
0.18
0.5
Reproducibility
2.11
0.49
1.7
ASTM D3792 ASTM D4017
Water content {%)
(GC analysis) (Karl Fischer)
Repeatability
2.60
1.79
1.0 1.7
Reproducibility
4.44
3.32
2.6 5.3
8 Precision values were not sufficiently homogeneous across products to permit pooling for a single estimate of
method precision. These results are presented solely to permit comparison with EPA Method 24.
b Square root of mean variance,
e Method 24 reports the relative standard deviation; for high total volatile content or water content this is
approximately the absolute standard deviation.
when the greater variability in composition for consumer products is considered. This
suggests that the Consumer Products Method provides results similar to those obtained with
EPA Method 24,
Examining the results by product (Table 4-6), it is seen that a few products have larger
values of repeatability and reproducibility. The cold cream (product SC) precision for total
volatiles may represent problems with sample dispersal in the drying dish. This product was a
somewhat viscous emulsion and may not have adequately spread over the bottom of the
aluminum pan used for drying. The addition of a suitable dispersion agent to get a more
uniform film may be useful for such products (this has not been tested).
The precision of the water analysis for windshield washer fluid (Product LA) is due to
two laboratories reporting values that were far from the mean of the other laboratories (one
laboratory was high and the other was low). The replicate analyses for all laboratories showed
good precision, as evidenced by the good value for repeatability (1.0 percent). The reason for
the differences among laboratories is not known. The only unusual feature of the windshield
washer fluid is its high methanol content (approximately 30 percent, added as an antifreeze).
It is possible that this caused chromatographic problems in the water analysis at these
laboratories, but this could not be verified.
32
-------
SECTION 5
QUALITY ASSURANCE AND QUALITY CONTROL
OVERVIEW
The design of this interlaboratory study provided a high level of quality assurance for
the resulting data set. Two important aspects in the study design which had a significant
impact on data quality were the study protocol and data review procedures. These are
described below.
Where applicable, the quality assurance/quality control plan which Radian developed
for their previous comparability study (6) was followed.
STUDY PROTOCOL
The study protocol (Appendix D) provided written instructions for participants in the
interlaboratory study, including:
* number of samples, replicates, and the order of analyses,
• method for analyzing products,
• reporting procedures (including forms used to report data), and
* contacts for resolution of any questions about the protocol, method, or
analyses.
DATA REVIEW
The data review activities are described in detail in Section 4 of this report. The
primary emphasis of the data review was the application of statistical techniques described in
ASTM E-691-87 (2) for the determination of outliers in the interlaboratory study data set.
Other statistical techniques (also described in Section 4) were also used to evaluate data
quality. Additional review activities included screening for missing and truncated data.
33
-------
REFERENCES
1. "Determination of Volatile Matter Content, Water Content, Density, Volume Solids,
and Weight Solids of Surface Coatings", Code of Federal Regulations. Title 40, Part
60, Appendix A, Method 24 (1985).
2. "Standard Practice for Conducting an Interlaboratory Study to Determine the Precision
of a Test Method", ASTM Designation E 691-87, American Society for Testing and
Materials, Philadelphia PA, 1988.
3. Taylor, J.K., Statistical Techniques For Data Analysis. Lewis Publishers, Chelsea MI,
1990, p. 92-93 and Table A.9.
4. Youden, W. J., "Ranking Laboratories by Round-Robin Tests", Precision
Measurement and Calibration. NBS Special Publication 300, 1969, pp. 165-1699, (this
is a reprint of Materials Research and Standards. American Society for Testing and
Materials, Philadelphia, PA, January 1964, pp. 9-13).
5. Steel, R.G.D., and J.H. Torrie, Principles and Procedures of Statistics. 2nd ed.,
McGraw-Hill Book Company, New York, 1980, pp. 471-472.
6. "Level 3 Quality Assurance Project Plan, Consumer Product Test Methods", Radian
Corporation, Revision 1, May 1993.
34
-------
APPENDIX A
DETERMINATION OF VOLATILE ORGANIC COMPOUNDS
IN CONSUMER PRODUCTS
Notice
Mention of trade names or commercial products does not constitute
endorsement or recommendation for use. Significant changes in the
method from the version used in the interlaboratory study are noted in
footnotes.
1.0 Applicability and principle
This method, based on EPA Method 24 (1) "Determination of Volatile
Matter Content, Water Content, Density, Volume Solids, and Weight Solids
of Surface Coatings", is used to determine the weight percent of volatile
organic compounds (VOCs) in a consumer product. A gravimetric technique
is used to determine total volatile content and a gas chromatographic (GC}
technique with thermal conductivity detection (TCD) is used to measure the
water content. The weight percent VOC is calculated as the difference
between the total volatile content and the water content. If exempt
compounds (CH4, etc.) and/or volatile inorganic compounds, other than water
(e.g., NH3), are present, their amount should be subtracted from the VOC
content as determined by this method to get a corrected VOC amount. The
analysis of exempt and non water volatile inorganic compounds is not
covered by this method.
A-1
-------
It is assumed that the personnel employing this method have sufficient
experience and training to properly evaluate and deal with any safety and
technical issues that might arise from this method's use. Although some
specific hazards have been noted, these do not represent all possible safety
problems that might arise. This method also assumes that the user is
familiar with general laboratory procedures and the analysis of compounds by
GC using a TCD.
1.1 Precision
An interlaboratory study was performed on a variety of consumer
products, including solid, liquid, aerosols, and foams. The VOC
measurements had a mean repeatability (within-laboratory precision) of 2.68
percent (as VOC) and a mean reproducibility (within- and between-laboratory
precision) of 4.41 percent (as VOC). No dense foams (e.g., shaving foam) or
products which are dispensed in an inverted position were included in the
results of this study.
2.0 Apparatus and materials
2.1 Apparatus and materials for total volatile content determination
2.1.1 Analytical balance
A balance with capacity sufficient to weigh sample vials
(approximately 100 g) to a precision of ± 0.0001 g.
A-2
-------
2.1.2 Drvina oven
A forced-draft oven capable of maintaining a temperature of 110
± 5 "C. This oven needs to be suitable for use with flammable vapors, if
flammable samples are to be evaluated.
2.1.3 Sample vials for aerosols, foams, and highly volatile liquids
A 100-mL glass serum vial with crimp-type cap and septum.
2.1.4 Sample pans for liquids, solids and gels
Aluminum weighing pans approximately 5.8 cm in diameter and 18
mm deep.
2.1.5 Desiccator
A desiccator with indicating desiccant (silica gel or calcium sulfate,
anhydrous} to store samples while they cool to room temperature.
2.1.6 Sample shaker (optional but recommended)
A wrist-action shaker with capacity to hold the product containers.
2.1.7 Transfer pi pets and spatulas
Pipets and laboratory spatulas suitable for transferring the product to
the sample vials or pans.
2.1.8 Thermometer
An oven thermometer capable of measuring 110 °C with an accuracy
of 1 °C.
A-3
-------
2.1.9 Aerosol sampling assembly
An aerosol can adapter (e.g., part no. 8048 from Alltech Associates or
equivalent) and a double-ended syringe needle used to connect the sample
vial to the adapter septum. This adapter is designed to fit over the exit tube
of an aerosol product (i.e., after the spray nozzle has been removed).
Obtaining samples from containers with one-piece exit tube/spray nozzles
will require a short length of appropriately sized plastic tubing to connect the
can to the adapter.
2.2 Apparatus and materials for determining water content
2.2.1 Dimethylformamide (DMFl
Dimethylformamide — anhydrous, GC, or spectrophotometry grade.
2.2.2 Isopropyl alcohol fIFA)
Isopropyl alcohol (also called isopropanol or 2-propanol), anhydrous
and free from any impurities that would interfere with analysis.
2.2.3 Isobutyl alcohol HBA)
Isobutyl alcohol (also called isobutanol or 2-methyl, 1 -propanol),
anhydrous and free from any impurities that would interfere with analysis.
2.2.4 Water
Water, high-performance liquid chromatography (HPLC) grade.
2.2.5 Gas chromatograph
A gas chromatograph with TCD and integrator (or data system).
A-4
-------
2.2.6 GC column
A column that will separate IPA, IBA, and water from each other and
from other consumer product components. A 6 ft by 1/8 in. stainless steel
column packed with 60/80 mesh Porapak Q has proven successful in this
application, although other columns may be used.
2.2.7 GC carrier gas
Helium, ultra-high-purity grade.
2.2.8 GC syringe
A 10-//L gas-tight syringe used to introduce samples into the gas
chromatograph.
2.2.9 Sample vials
A 15-mL glass vial with screw cap.
2.2.10 Svrinae filters (optional)
Syringe filters to permit filtering of any particles from the sample
solutions before GC injection.
3.0 Procedure for determining total volatile content
The procedure for determining total volatile content of consumer
products is divided into three sections based on physical properties. These
sections are: aerosols (propellent pressurized) and foams, gels and solids, and
liquids (including pump aerosols). Sheets for data entry are provided at the
end of this method.
A-5
-------
3,1 Aerosols and foams
WARNING - EXPLOSION HAZARD: This procedure
uses glass vials under pressure. Wear appropriate
eye and face protection.
3.1.1 Step 1
Select and label two 10O-mL glass vials with crimp caps and septa.
Weigh each vial separately and record the weight to the nearest 0.0001 g as
"A" on the data sheet. Affix the caps and septa and securely crimp the
caps. Reweigh the vials with caps and septa attached and record the
weights as "B" on the data sheet. Because the two vials will have slightly
different weights, it is important to identify correctly which vial is used for
which sample.
3.1.2 Step 2
Mix the consumer product thoroughly by shaking the container
vigorously for 1 to 2 min. Shaking should be performed with a wrist-action
shaker (preferred method} or by hand. (NOTE: Aerosol and foam products
contain an eductor tube that may be filled with propellant until the can is first
used. Press the sample valve to dispense a short [about 1 sec] burst of
product to clear the eductor tube before continuing the sampling procedure.
This step should be needed only upon initial use of the product, i.e., after
initial purchase.)
A-6
-------
3.1.3 Step 3
NOTE: Some containers may have a one-piece spray nozzle and exit
tube. These containers require addition of an exit tube to the sampling
adapter before the adapter can be connected to the container.
Immediately after shaking the container, insert one end of the double-
sided needle into the aerosol sampling adapter. Remove the spray nozzle
from the aerosol or foam container and connect the sampling adapter to the
exit tube of the valve (i.e., in the place of the spray nozzle).
3.1.4 Step 4
With the product container oriented to dispense product1 (upright for
products whose instructions specify upright use, inverted for products that
specify inverted use), insert the other end of the needle through the septum
on the glass vial. Depress the adapter, opening the container valve for a
sufficient time to allow about 0.5 g of sample into the vial. While
maintaining a firm seal between the adapter and the exit tube, release
pressure on the adapter to close the container's valve. Quickly pull the
adapter needle out of the vial septum, so as to lose as little propellant as
possible. (NOTE: A hissing sound will result as some gas escapes from the
1 The method used in the interlaboratory study specified an upright position for
sampling. This is inappropriate for products that are used in an inverted position,
e.g. carpet cleaner.
A-7
-------
adapter assembly.) Reweigh the pressurized vial and record the weight to
the nearest 0,0001 g as "C" on the data sheet.
3.1.5 Step 5
Reshake the container. Collect a second aliquot in the second sample
vial, as described in steps 3 and 4 above.
3.1.6 Step 6
Use the double-ended needle to gently bleed propellant from the vials.
Take care not to bleed too rapidly or nonvolatile contents may be blown out
through the needle. Swirl gently to dislodge any propellant pockets and
bleed any remaining pressure.
WARNING: Glass vials under pressure may
explode. Be certain to bleed off all pressure before
attempting to remove the crimp caps.
Remove the caps and septa from both sample vials and heat the vials in the
drying oven at 11 0 ± 5 °C for 1 h. After heating, remove the sample vials
from the oven, place in the desiccator to cool to ambient temperature, and
weigh. Record the weights as "D" on the data sheet.
3.1.7 Step 7
Clean the adapter with a suitable solvent between each set of
products. Disassemble and allow the adapter to dry completely before reuse.
3.2 Gels and solids
3.2.1 Step 1
A-8
-------
Weigh an aluminum sample pan and record the weight to the
nearest 0.0001 g as "E" on the data sheet.
3.2.2 Step 2: Gels in tube containers
Mix the product thoroughly by kneading the tube for 1 to 2 min before
sampling. Dispense approximately 0.5 g of product into the weighing pan by
squeezing the container from the bottom of the tube and forcing the product
out of the tube opening. Weigh the pan and sample and record the weight to
the nearest 0.0001 g as "F" on the data sheet.
3.2.3 Step 2: Other gels
Mix thoroughly by gently stirring the gel with a laboratory spatula or
stirring rod for 1 to 2 min. Transfer approximately 0.5 g of product to the
weighing pan using a laboratory spatula. Weigh the pan and sample and
record the weight to the nearest 0.0001 g as "F" on the data sheet.
3.2.4 Step 2: Granular solids
Mix granular solids thoroughly by shaking for 1 to 2 min with a wrist-
action shaker {preferred method) or by hand. Transfer approximately 0.5 g
of product to the weighing pan using a laboratory spatula. Weigh the pan
and sample and record the weight to the nearest 0.0001 g as "F" on the
data sheet.
A-9
-------
3.2.5 Step 3
Repeat this procedure (steps 1 through 3} for a total of two sample
aliquots from the same container.
3.2.6 Step 4
Place the sample pans, containing the sample, in the oven at 110
± 5 °C for 1 h. After heating, remove the pans from the oven, place in the
desiccator to cool to ambient temperature, and weigh to the nearest
0.0001 g. Record the weight as "Q" on the data sheet.
3.3 Liquids
3.3.1 Sten 1
Weigh an aluminum sample pan and record the weight to the
nearest 0.0001 g as "E" on the data sheet.
3.3.2 Step 2
Mix the product thoroughly by shaking the container for a minimum of
5 min. Use a wrist-action shaker (preferred method) or shake by hand.
3.3.3 Step 3
Immediately after mixing, use a pipet to transfer approximately 0.5 g
of sample into the aluminum pan, and weigh. Record the weight to the
nearest 0.0001 g as "F" on the data sheet.
If the sample loses weight too rapidly when open to the air (i.e., the
balance will not provide a stable reading), it will be necessary to use a
capped glass vial in place of the aluminum pan. Weigh a 100-mL glass vial
A-10
-------
both with and without the cap and septum, and record the weights (as "A"
and "B"f respectively on the data sheets). Remove an aliquot of sample
using a pipet and load the sample into the glass vial. Cap the vial and weigh.
Record the weight to the nearest 0.0001 g as "C" on the data sheet.
3.3.4 Step 4
Mix the product thoroughly by shaking the container by hand for
approximately 1 to 2 min. Repeat steps 1 and 3 to take a second aliquot.
3.3.5 Step 5
Heat the oven to 110 ± 5 °C. Remove the caps from the vials {if
used) and place the vials or aluminum pans in the oven for 1 h. After
heating, remove the samples from the oven, place in the desiccator to cool to
ambient temperature, and weigh. Record the weight to the nearest 0.0001 g
as "G" on the data sheet for pans or as "D" for vials.
4.0 Procedure for determining water content
This procedure assumes that the user is familiar with analysis by gas
chromatographic methods. Details of instrument operation will vary with the
individual apparatus and are not specified in this method.
Two internal standards {IPA and IBA) are added to all samples and
calibration standards. The I PA standard is used for all calculations unless the
response ratio of I PA to IBA for the samples is significantly different from the
ratio for the calibration samples (see section 5.2.1.8). If this is the case,
A-11
-------
then IBA is used as the internal standard. The response factor for water will
depend on which internal standard is used and cannot be determined until
standards and samples have been run.
4.1 Chromatographic conditions
A column and chromatographic conditions should be selected to
separate IPA, IBA, and water from each other and from other product
components. The following conditions have proven suitable in tests of this
method and may be used as a starting point.
4.1.1 GC column
As described in section 2.2.6 above.
A-12
-------
4.1.2 Flow rate
Set the flow rate to 30 mL/min.
4.1.3 Injector temperature
Set the injector temperature to 300 °C.
4.1.4 Qveri temperature
Set the GC overi temperature to 200 °C (isothermal).
4.1.5 Detector temperature
Set the detector temperature to 250 °C.
4.2 Calibration
4.2.1 Calibration standards
Weigh six 1 5-mL glass vials with caps. Record the weight to the
nearest 0.0001 g and enter the weights as "H" on the data sheet. Add
approximately 0.1, 0.2, 0.3, 0.4, and 0.6 g HPLC-grade water into
successive vials and record the weight of each vial after addition of water as
"I" on the data sheet.
Weigh 0.2 g I PA into each vial. Record the weight to the nearest
0.0001 g and enter as "K" on the data sheet. Add 0.2 g IBA into each vial.
Weigh and record the weight to the nearest 0.0001 g as "L" on the data
sheet. Weigh a 3-mL volume of DMF into each vial. Record the weight to
the nearest 0.0001 g as "M" on the data sheet.
A-13
-------
4.2.2 Blank
Prepare a blank in the same way as the calibration standards (section
4.2.1), omitting the water.
4.2.3 Analysis
Analyze the calibration standards and blank by GC, using a 1-//L
injection. Record the water, isopropanol, and isobutanol responses as "N,"
"0," and "P," respectively, on the data sheet.
4.3 Sample analysis
4.3.1 Step 1: Gels, solids, and liquids
Prepare gels, solids, and liquid samples using a 1 5-mL vial. Weigh the
glass vial and cap to the nearest 0.0001 g and record the weight as "Q" on
the data sheet. Mix and dispense the samples as described in the total
volatile procedure (section 3.0). Add approximately 0.5 g of sample into the
vial. Weigh the vial, cap, and sample and record the weight to the
nearest 0.0001 g in both "R" and "S" on the data sheet.
4.3.2 Step 1: Aerosols and foams
Preweigh a 100-mL glass vial, with the caps and septa, to the
nearest 0.0001 g and record the weight as "Q" on the data sheet. Mix and
dispense the samples as described in section 3.1. (NOTE: Aerosol and foam
products contain an eductor tube that may be filled with propellant until the
can is first used. Press the sample valve to dispense a short [about 1 sec]
burst of product to clear the eductor tube before continuing the sampling
A-14
-------
procedure. This step should be needed only upon initial use of the product,
i.e., after initial purchase.)
Record weight to the nearest 0.0001 g as "R" on the data sheet.
Gently bleed the propellant, using a syringe needle. Take care not to bleed
too rapidly or nonvolatile contents may be blown out of the needle. Swirl
gently to dislodge any propellant pockets and bleed any remaining pressure.
WARNING - Glass vials under pressure may
explode. Be certain to bleed off all pressure before
handling vials further or disposing of them.
Reweigh the vials after bleeding the propellant to the nearest 0.0001 g
and record the weight as "S" on the data sheet. Clean the adapter with a
suitable solvent between each set of products. Disassemble and allow the
adapter to dry completely before reuse.
4.3.3 Step 2
Add 0.2 g IRA and 0.2 g IBA as internal standards and add 3 mL DMF.
Record the weight after each addition to the nearest 0.0001 g on the data
sheet as "T," "U," and "V," respectively.
4.3.4 Step 3
Repeat the entire procedure (steps 1 and 2) to prepare a total of two
aliquots.
A-15
-------
4.3.5 Step 4
NOTE: If samples appear cloudy or have sediment, it may be necessary
to filter the solutions through a syringe filter before GC injection. In addition,
if samples have been stored in the refrigerator, sonicate them for 1 5 min and
allow to warm to room temperature before injection.
Analyze the samples by GC using a 1-/iL injection. Record the water,
isopropanol, and isobutanol area amounts from the data acquisition system
as "W," "X," and "Y," respectively.
4.4 Quality control procedures
Analyze a calibration standard and blank after every eight sample
injections. The response factor should not vary by more than 10% from a
previous response factor on the same day or more than 20% between days.
If the response factor is outside of these limits, then prepare a new set of
calibration standards and recalibrate.
5.0 Calculations
5.1 Total volatile content
A-16
-------
5.1.1 Sample weight
5.1.1.1 Aerosols, foams, and highly volatile liquids. The initial sample
weight (SW) is calculated as:
SW = C - B
where
C = weight of filled vial, cap, and septum
B = weight of empty vial, cap, and septum.
5.1.1.2 Gels, solids, and liquids. The initial sample weight {SW) is
calculated as:
SW = F - E
where
F = weight of filled aluminum pan
E = weight of empty aluminum pan.
5.1.2 Final sample weight after heating
5.1.2.1 Aerosols, foams, and highly volatile liquids. The final sample weight
after heating (FW) is calculated as:
FW ~ D A
where
D - weight of filled vial after heating
A = weight of empty vial.
A-17
-------
5.1.2.2 Gels, solids, and liquids. The final sample weight after heating (FW)
is calculated as;
FW = G - E
where
G - weight of the filled aluminum sample pan after heating
E = weight of the empty aluminum sample pan.
5.1.3 Total volatile content
The total volatile content (TV) is calculated as;
TV (%) = (SW - FW) x 1Q0
SW
where
SW = initial sample weight (section 5.1.1)
FW = final sample weight after heating (section 5.1.2).
5.1.4 Average total volatiles
The average total volatiles (ATV) is calculated as:
^ jy = "^sample 1 + "^sample 2
2
where
TV = total volatiles (section 5.1.3).
5.2 Water content
Note that only one of the two compounds (IPA and !BA) added to the
samples will be used as an internal standard. The appropriate internal
standard is selected after both calibration standards and samples have been
analyzed (see section 5.2.1.8 for criteria).
A-18
-------
5.2.1 Calibration standards
5.2.1.1 Water weight. The weight of water added to each calibrati
standard (WW) is calculated as:
WW = I - H
where
I = weight of water, vial, and cap
H = weight of empty vial and cap.
5.2.1.2 IPA weight. The weight of isopropanol added to each calibration
standard (WIPA) is calculated as:
WIPA = K - I (for samples), or
WIPA = K H (for blank)
where
K = weight after IPA addition
I or H - weight before IPA addition,
5.2.1.3 IBA weight. The weight of isobutanol added to the calibration
standard (WIBA) is calculated as:
WIBA L K
where
L = weight of vial, cap, and contents after IBA addition
K = weight before IBA addition.
A-19
-------
5.2.1.4 DMF weight. The weight of DMF added to the calibration standard
(WDMF) is calculated as:
WDMF - M - L
where
L = weight before DMF addition
M = weight after DMF addition.
5.2.1.5 IPA-to-lBA response ratio. The I PA-to-1BA response ratio is
calculated2 for each standard as;
O
PBR =«!£*.
WIBA
where
O = IPA area count
WIPA = IPA weight (section 5.2.1.2)
P = IBA area count
WIBA = IBA weight (section 5.2.1.3).
2 The method version sent to participants in the interlaboratory study did not
divide the areas by the compound weight. Correcting for the amount of IPA and
IBA added improves the ability of the method to detect small amounts of IPA in
products.
A-20
-------
5.2.1.6 Average IPA-to-IBA response ratio. The average IPA-to-IBA
response ratio (AVR) is calculated as:
n
£ PBR,
AVR = '~1
n
where
PBR| = response ratio of IPA to IBA for calibration standard i
n = number of calibration standards (i.e., 5).
5.2.1.7 Standard deviation of IPA-to-IBA response ratio. The standard
deviation of the IPA-to-IBA response ratio (SDR) is calculated as:
SDR
£ (PBR; - AVR):
i = <|
n - 1
where
AVR = average ratio of IPA response to IBA response
PBR. = ratio of IPA to IBA for calibration standard i
n = number of calibration standards (i.e., 5).
5.2.1.8 Highest acceptable IPA-to-IBA response ratio. The highest
acceptable response ratio (HR) for which IPA may be used as the internal
standard is calculated as:
HR = AVR + (3 x SDR)
where
AVR = average IPA to IBA response ratio
SDR = standard deviation of AVR.
A-21
-------
5.2,1.9 Response factor for water. The response factor for water (RF) is
calculated for each calibration standard as:
WIPA x (N. - Nh. .)
RF = ! (for I PA as internal standard),
WW * O
WIBA x (N. - Nh1ank)
or RF = — (for IBA as internal standard)
WW x P
where
WIPA - weight of (PA in calibration standard
WIBA - weight of IBA in calibration standard
WW = weight of water in calibration standard
Nj = area count for water in standard i
Nhl,„ „ - area count for water in blank
blariK
O = area count for IPA
P = area count for IBA.
A-22
-------
5.2.1.10 Water content of DMF blank. The weight percent of water
contained in the DMF blank (WB) is calculated as:
100 x WIPA x N ,, ... . . . . . ..
WB = (for IPA as internal standard),
O x WDMF x RF
or WB = * WlBA_x_N_ (for IBA as internal standard).
P X WDMF X RF
where
WIPA = weight of IPA in blank
WIBA - weight of IBA in blank
N = area count for water in blank
O = area count for IPA in blank
P = area count for IBA in blank
WDMF = weight of DMF in blank
RF = Response factor for water.
5.2.2 Samples
5.2.2.1 Sample weight. The sample weight (SW2) is calculated as:
SW2 R - G
where
R - weight of sample, vial, and cap
Q = weight of empty vial and cap.
A-23
-------
5.2.2.2 Isopropanol weight. The weight of isopropanol added to the sample
(SIPA) is calculated as:
SIPA = T - S
where
T = weight of vial, cap, and contents after IPA addition
S = weight before IPA addition.
5.2.2.3 Isobutanol weight. The weight of isobutanol added to the sample
(SIBA) is calculated as:
SIBA = U - T
where
U = weight of vial, cap, and contents after IBA addition
T = weight before IBA addition,
5.2.2.4 DMF weight. The weight of DMF added to the sample (SDMF) is
calculated as:
SDMF - V U
where
V = weight of vial, cap, and contents after DWIF addition
U = weight before DMF addition.
A-24
-------
5.2.2.5 IPA-to-IBA response ratio. The IPA-to-IBA response ratio is
calculated as:
X
PBR =
Y
WIBA
where
X = IPA area count
Y = IBA area count
WIPA = weight of IPA in sample
WIBA = weight of IBA in sample.
If PBR for the samples does not exceed the highest acceptable ratio (HR,
section 5.2.1.8) then use IPA as the internal standard in all calculations;
otherwise, use IBA as the internal standard.
A-25
-------
5.2.2.6 Weight percent water (uncorrected for DMF). The weight percent
water in the sample not corrected for DMF (WWU) is calculated as:
. 100 x W x SIPA .. . . . . . .
WWU = (for IPA used as internal standard)
X x SW2 x RF
....... - 100 x W x SIBA , . . , . .
or WWU = (for IBA used as internal standard)
Y x SW2 x RF
where
SIPA = weight of IPA in sample
SIBA = weight of IBA in sample
W = area of water peak
X = area of IPA peak
SW2 = sample weight
Y = area of IBA peak
RF = response factor for water.
NOTE; Use the response factor (RF) for water from the standard that has
the nearest water peak area compared to the sample's water peak area.
A-26
-------
5.2.2.7 Percent water corrected for DMF blank. The percent water in the
sample, corrected for the DMF blank (WWF), is calculated as;
WWF = WWU - WB * SDMF
SW2
where
WWU = weight percent water uncorrected for DMF blank
WB = weight percent water present in DMF blank
SDMF = weight of DMF added to sample
SW2 = sample weight.
5.2.2.8 Average percent water by weight. The average percent water by
weight (AWF), corrected for DMF blank, is calculated as:
WWF . . + WWF . „
AWF sample 1 sample 2
2
where
WWF = weight percent of water, corrected for DMF (section 5.2.2.7).
5.3 Weight percent VOC
The total weight percent of volatile organic compounds (VOCs) in the
consumer product is calculated by:
VOC = ATV - AWF
where
ATV = average total volatiles
AWF = average water fraction.
A-27
-------
6.0 References
1. "Determination of Volatile Matter Content, Water Content, Density,
Volume Solids, and Weight Solids of Surface Coatings", Code of
Federal Regulations, Title 40, Part 60, Appendix A, Method 24.
A-28
-------
Determination of Volatile Organic Content of Consumer Products
Part I: Total Volatile Content Determination
Data Sheet for Aerosols, Foams and Highly Volatile Liquids
Laboratory Name:
Analyst's Name;
Product ID:
Analysis Date:
Sample Weighings
Aliquot 1
Aliquot 2
Empty Vial (± 0.0001 g)
Empty Vial, Cap, and Septum (± 0.0001 g)
Filled Vial, Cap and Septum (+ 0.0001 g)
Filled Vial AFTER HEATING (± 0.0001 g)
Oven Data
Temperature (± 1°C)
Time samples placed in oven
Time samples removed from oven
Calculations
1.0000
2.0000
SW
Sample Weight (g) = C - B
FW
Final Sample Weight (g) = D - A
TV
Total Volatile Loss (%) = (SW - FW) / SW * 100
Total Volatile Content Results
ATV
Average Total Volatile Loss (%) {Section 5.1.4)
A-29
-------
Determination of Volatile Organic Content of Consumer Products
Part I; Total Volatile Content Determination
Data Sheet for Gels, Solids, and Liquids
Laboratory Name:
Analyst's Name:
Product ID:
Analysis Date:
Sample Weighings
Aliquot 1
Aliquot 2
Empty Aluminum Pan(+ 0.0001 g)
Filled Aluminum Pan (± 0,0001 g)
Filled Pan AFTER HEATING (± 0,0001 g)
Oven Data
Temperature (± 1X)
Time samples placed in oven
Time samples removed from oven
Calculations
1.0000
2.0000
SW
Sample Weight (g) = F ~ E
FW
Final Sample Weight (g) = G - E
TV
Total Volatile Loss (%) = (SW - FW) / SW * 100
Total Volatile Content Results
AW
Average Total Volatile Loss (%) (Section 5.1.4)
A-30
-------
Determination of Volatile Organic Content of Consumer Products
Part II; Water Content Determination (Page 1 of 2)
Data Sheet for All Sample Types
Laboratory Name;
Analyst's Name;
Sample Id;
Analysis Date;
Laboratory ID(optional):
Sample Weighings
Q
Weight of empty vial and cap (± 0,0001 g)
R
Weight of vial and cap plus sample (± 0.0001 g)
S
Weight after propellant released {+ 0.0001 g) = R
T
Weight after isopropanoi (IPA) addition (± 0.0001
U
Weight after isobutanol (IBA) addition (±
V
Weight after DMF addition (± 0.0001 g)
Sample Weight Calculations
0
0
SW2
Sample weight (g) = R - Q
SI PA
Weight of Isopropanoi (g) = T - S
SIBA
Weight of Isobutanol (g) = U - T
SDMF
Weight of DMF (g) = V - U
GC Analysis
0
0
W
Water area
X
IPA area
Y
IBA area
Select Internal Standard
0
0
PBR
IPA to IBA ratio = X/Y
Highest Acceptable Ratio (Enter HR from Calibration Data Sheet)
Is either Aliquot's Ratio greater than Highest Acceptable Ratio (Yes/No)?
If Yes then use IBA as internal standard, otherwise use IPA as internal standard.
A-31
-------
Determination of Volatile Organic Content of Consumer Products
Part II: Water Content Determination (Page 2 of 2)
Data Sheet for All Sample Types
Laboratory Name:
Analyst's Name:
Sample Id:
Analysis Date:
Weight Percent Water Calculations
1
2
RF
Enter appropriate RF from Calibration Data
Sheet (see Section 5,2.2,6)
WWU
Water weight percent not corrected for DMF blank
1
2
a) if IPA used as internal standard
WWU = 100 * W* SIPA/ (X * SW2 * RF)
b) if IBA used as internal standard
WWU = 100 * W * SIBA / ( Y* SW2 * RF)
WB
Weight Percent Water for DMF Blank (from Calibration Data Sheet)
WWF
Weight percent of water corrected for DMF
blank WWF = WWU - (WB * SPMF) ISW2
AWF
Average percent water (corrected for DMF blank)
(Section 5.2,2.8)
Part III: Volatile Organic Content Determination
VOC
Volatile Organic Content (%) = ATV - AWF
A-32
-------
Determination of Volatile Organic Content of Consumer Products
Calibration for Water Content Determination (Page 1 of 3)
Laboratory Name;
Analyst's Name;
Analysis Date;
Laboratory ID (optional): [ | ] | |
Standard Preparation Blank Std 1 Std 2 Std 3 Std 4 Std 5
> H
L
M
Weight Calculations Blank Std 1 Std 2 Std 3 Std 4 Std S
WW
WIPA
WIBA
WDMF
Weight of empty vial and cap (± 0.0001 g) I
Weight of vial and cap plus water (± 0.0001 g) NA
Weight after isopropanol (IPA) addition (± 0,0001 g)l
Weight after isobutanol (iBA) addition (± 0,0001 g) j
Weight after DMF addition (± 0.0001 g) |
Water (g) = I - H
NA
(PA (g) = K -1 (or H for blank)
IBA (g) = L - K
DMF (g) = M -1.
-------
Determination of Volatile Organic Content of Consumer Products
Calibration for Water Content Determination (Page 2 of 3)
Laboratory Name:
Analyst's Name;
Analysis Date:
GC Analysis
Blank
Std 1
Std 2
Std 3
Std 4
Std S
Water area
IPA area
IBA area
IPA I IBA Ratio Calculation
Blank
Std 1
Std 2
Std 3
Std 4
Std S
IPA to IBA ratio = (O/WIPA) I (P/WIBA)
{Highest Acceptable IPA I IBA Ratio
Calculation
AVR
SDR
Average PBR (excludes blank) {section 5,2,1.6)
Standard Deviation of PBR (excludes blank)
{section 5.2.1.7)
Highest Acceptable PBR to use IPA as internal
standard = AVR + 3 * SDR
-------
Determination of Volatile Organic Content of Consumer Products
Calibration for Water Content Determination (Page 3 of 3)
Laboratory Name;
Analyst's Name:
Analysis Date:
Response Factor Calculations
Std 1 Std 2
Std 3
Std 4
Std §
a) For IPA as internal standard
RF = WiPA * (N - N for blank) / (WW * 0)
b) For IBA as internal standard
RF = WIBA * ( N - N for blank) / (WW * P)
Water Content of DMF blank (weight
percent)
a) IPA used as internal standard
WB = 100 *N for blank * WIPA for blank / { O for blank * WDMF
for blank * RF)
b) IBA used as internal standard
WB = 100 * N for blank * WIBA for blank / ( P for blank * WDMF
for blank * RF)
-------
APPENDIX B
LABORATORY RESULTS1
1 Laboratory codes were randomly assigned and do not reflect the order in
Table 3-2. Although the code letter used by each laboratory is not revealed in this
report, the same code letter was used to refer to a given laboratory throughout the
study and this report.
B-1
-------
LA - Windshield Washer Fluid
Lab Number
Total
Water
Internal
VOC <%)
Volatiles (%)
Content (%)
Standard
A 1
99.97
95.96
I PA
4.01
2
99.97
95.22
I PA
4.75
3
99.98
95.05
I PA
4.93
average
99.97
95.41
4.56
std. dev.
0.01
0.48
0.49
B 1
100.02
69.72
I PA
30.30
2
99.98
71.21
I PA
28.77
3
99.98
71.93
iBA
28.05
average
99.99
70.95
29.04
std. dev.
0.02
1.13
1.15
D 1
99.90
70.60
I PA
29.30
2
99.89
74.23
I PA
25.66
3
99.95
70.02
IPA
29.93
average
99.91
71.62
28.30
std. dev.
0.03
2.28
2.31
E 1
100.00
66.21
IPA
33.79
2
100.00
65.21
IPA
34.61
3
100.00
65.30
IPA
34.70
average
100.00
65.57
34.37
std. dev.
0.00
0.55
0.50
F 1
99.95
68.20
IPA
31.75
2
100.00
67.79
IPA
32.21
3
100.00
69.09
IPA
30.91
average
99.98
68.36
31.62
std. dev.
0.03
0.66
0.66
G 1
99.92
51.98
IPA
47.96
2
100.03
51.95
IPA
48.05
3
100.00
52.76
IPA
47.24
average
99.98
52.23
47.75
std. dev.
0.06
0.46
0.44
H 1
100.01
68.03
IPA
31.98
2
100.01
67.62
IPA
32.39
3
99.99
68.69
IPA
31.30
average
100.00
68.11
31.89
std. dev.
0.01
0.54
0.55
J 1
99.96
70.91
IPA
29.06
2
99.97
71.73
IPA
28.24
3
99.96
70.01
IPA
29.95
average
99.96
70.88
29.08
std. dev.
0.00
0.86
0.85
B-2
-------
LB - Laundry Frewash
Lab Number
Total
Water
Internal
VOC {%)
Volatiles {%) Content (%}
Standard
A 1
89.80
89.22
I PA
0.58
2
90.08
89.02
I PA
1.07
3
90.08
88.99
I PA
1.99
average
89.99
89.08
1.21
std. dev.
0.16
0.13
0.72
B 1
90.17
91.13
I PA
-0.96
2
90.14
90.90
I PA
-0.76
3
90.08
91.71
I PA
-1.63
average
90.13
91.25
¦1.12
std. dev.
0.05
0.42
0.46
D 1
90.02
91.15
I PA
-1.13
2
90.05
91.89
I PA
-1.84
3
90.11
78.54*
IPA
11.59
average
90.06
87.19
2.87
std. dev.
0.04
7.50
7.56
E 1
90.12
90.35
I PA
-0.23
2
90.09
91.51
IPA
-1.42
3
90.09
97.70
IPA
-7.61
average
90.10
93.19
-3.09
std. dev.
0.02
3.95
3.96
F 1
90.11
90.98
IPA
-0.87
2
90.14
88.84
IPA
1.30
3
90.10
90.46
IPA
-0.36
average
90.12
90.09
0.02
std. dev.
0.02
1.12
1.13
G 1
90.22
86.34
IPA
3.89
2
90.13
86.96
IPA
3.17
3
90.13
85.99
IPA
4.14
average
90.16
86.43
3.73
std. dev.
0.05
0.49
0.50
H 1
90.18
89.61
IPA
0.57
2
90.18
89.48
IPA
0.70
3
90.24
90.08
IPA
0.16
average
90.20
89.72
0.48
std. dev.
0.03
0.32
0.28
J 1
90.21
86.58
IPA
3.63
2
90.28
88.50
IPA
1.77
3
90.16
90.80
IPA
-0.64
average
90.22
88.63
1.59
std. dev.
0.06
2.11
2.14
1 Individual aliquot values were 70.2 and 86.9 percent water content.
B-3
-------
LC - Hairspray (pump type)
Lab Number
Total
Water
Internal
VOC (%)
Volatifes (%)
Content {%)
Standard
A 1
94.59
13.84
iPA
80.75
2
94.59
13.23
I PA
81.36
3
94.56
13.38
IPA
81.19
average
94.58
13.48
81.10
std, dev.
0.02
0.32
0.31
B 1
94.16
15.45
IBA
78.71
2
94.12
17.42
IPA
76.69
3
94.16
16.09
IPA
78.07
average
94.15
16.32
77.82
std. dev.
0.02
1.01
1.03
D 1
94.17
13.38
IPA
80.79
2
94.23
13.80
IPA
80.43
3
94.27
12.92
IPA
81.35
average
94.22
13.37
80.86
std. dev.
0.05
0.44
0.46
E 1
94.40
13.53
IPA
80.87
2
94.25
14.31
IPA
79.94
3
94.27
12.97
IPA
81.30
average
94.31
13.60
80.70
std. dev.
0.08
0.67
0.70
F 1
94.00
13.32
IPA
80.68
2
94.07
29.16
IPA
64.91
3
93.94
12.62
IPA
81.33
average
94.00
18.37
75.64
std. dev.
0.07
9.36
9.30
G 1
94.27
13.32
IPA
80.95
2
94.07
12.77
IPA
81.30
3
94.11
13.29
IPA
80.81
average
94.15
13.13
81.02
std. dev.
0.10
0.31
0.25
H 1
94.22
14,16
IPA
80.06
2
94.34
14.01
IPA
80.33
3
94.25
14.10
IPA
80.15
average
94.27
14.09
80.18
std. dev.
0.06
0.08
0.14
J 1
93.94
13.97
IPA
79.98
2
94.01
14.14
IPA
79.87
3
93.80
14.03
IPA
79.77
average
93.92
14.05
79.87
std. dev.
0.11
0.09
0.10
B-4
-------
LP - Liquid Glass Cleaner
Lab Number
Total
Water
Internal
VOC (%)
Volatiles {%)
Content (%)
Standard
A 1
99.83
91.10
IBA
8.73
2
99.84
91.14
IBA
8.70
3
99.81
91.14
IBA
8.67
average
99.83
91.13
8.70
std. dev.
0.02
0.02
0.03
B 1
99.90
93.55
I PA
6.35
2
99.82
93.35
IBA
6.47
3
99.85
93.27
IBA
6.58
average
99.86
93.39
6.47
std. dev.
0.04
0.14
0.12
D 1
99.77
89.58
IBA
10.19
2
99.81
94.23
IBA
5.58
3
99.87
92.06
IBA
7.81
average
99.82
91.96
7.86
std. dev.
0.05
2.33
2.31
E 1
99.87
93.86
IBA
6.01
2
99.86
93.61
IBA
6.22
3
99.83
90.15
IBA
9.68
average
99.85
92.54
7.30
std. dev.
0.02
2.07
2.06
F 1
99.92
94.41
IBA
5.51
2
99.86
91.71
IBA
8.15
3
99.84
93.53
IBA
6.31
average
99.87
93.22
6.66
std. dev.
0.04
1.38
1.35
G 1
99.85
76.41
I PA
23.37
2
99.88
77.81
I PA
22.07
3
99.90
79.99
I PA
19.91
average
99.88
78.07
21.78
std. dev.
0.03
1.80
1.75
H 1
99.82
82.08
I PA
17.75
2
99.89
83.08
I PA
16.81
3
99.90
83.10
I PA
16.80
average
99.87
82.76
17.12
std. dev.
0.04
0.59
0.54
J 1
99.79
74.93
I PA
24.86
2
99.83
88.44
IBA
11.40
3
99.84
90.02
IBA
9.82
average
99.82
84.46
15.36
std. dev.
0.03
8.29
8.27
-------
SA - Stick Deodorant
Lab
Number
Total
Water
Internal
VOC{%)
Volatiles (%)
Content {%)
Standard
A
1
56.04
-0.40
I PA
56.44
2
57.18
0.01
I PA
57.17
3
55.85
0.36
I PA
55.48
average
56.36
-0.01
56.36
std. dev.
0.72
0.38
0.85
B
1
52.04
2.22
I PA
49.82
2
50.91
4.55
I PA
46.36
3
51.67
3.02
I PA
48.65
average
51.54
3.26
48.28
std, dev.
0.58
1.18
1.76
D
1
53.69
0.15
I PA
53.54
2
52.50
0.79
I PA
51.71
3
54.04
0.96
I PA
53.08
average
53.41
0.63
52.78
std. dev.
0.81
0.43
0.95
E
1
50.36
0.90
I PA
49.46
2
50.05
1.55
I PA
48.50
3
50.03
1.60
I PA
48.43
average
50.15
1.35
48.80
std. dev.
0.19
0.39
0.58
F
1
51.12
1.18
I PA
49.94
2
51.24
1.04
I PA
50,20
3
50.23
1.00
I PA
49.23
average
50.86
1.07
49.79
std. dev.
0.55
0.09
0.50
G
1
52.79
water was riot detected
2
52.43
3
52.65
average
52.62
std. dev.
0.18
H
1
53.64
water detected below analytical
2
53.32
detection
limit - no analysis
3
53.12
performed
average
53.36
std. dev.
0.26
J
1
54.99
0.35
(PA
54,64
2
56.06
0.71
IPA
55.35
3
56.24
0.85
IBA
55.39
average
55.76
0.64
55.12
std. dev.
0.67
0.25
0.42
B-6
-------
SB - Tile Cleaner
Lab Number Total Water Internal VOC (%)
Volatiles {%) Content (%) Standard
A
1
2
3
0.84
0.78
0.85
-0.32
0.13
0.00
IPA
IPA
tPA
1.16
0.66
0.85
average
std. dev.
0.82
0.04
-0.06
0.23
0.89
0.25
B
1
2
3
0.80
0.59
0.68
0.85
1.07
1.14
IPA
IPA
IBA
-0.05
-0.48
-0.46
average
std. dev.
0.69
0.11
1.02
0.15
-0.33
0.24
D
1
2
3
0.78
0.81
0.79
0.24
0.25
0.11
IPA
IPA
IPA
0.54
0.56
0.68
average
std. dev.
0.79
0.02
0.20
0.08
0.59
0.08
E
1
2
3
0.38
0.26
0.25
0.78
1.17
1.12
IPA
IPA
IPA
-0.40
-0.91
-0.87
average
std. dev.
0.30
0.07
1.02
0.21
-0.73
0.28
F
1
2
3
0.76
0.73
0.42
0.25
0.20
0.37
IPA
IPA
IPA
0.51
0.53
0.05
average
std, dev.
0.64
0.19
0.27
0.09
0.36
0.27
G
1
2
3
0.80
0.82
0.49
water was not detected
average
std. dev.
0.70
0.19
H
1
2
3
0.91
0.83
0.87
water detected below analytical
detection limit - no analysis
performed
average
std. dev.
0.87
0.04
J
1
2
3
0.77
0.82
0.54
0.44
0.73
0.62
IPA
IPA
IPA
0.33
0.09
-0.08
average
std. dev.
0.71
0.15
0.60
0.15
0.11
0.21
B-7
-------
SC - Cold Cream
Lab Number
Total
Water
Internal
VOC (%}
Volatiles {%)
Content {%}
Standard
A 1
39.55
35.30
IPA
4.25
2
41.05
30.28
IPA
10.78
3
42.36
32.94
IPA
9.42
average
40.99
32.84
8.15
std. dev.
1.41
2.51
3.45
B 1
34.66
33.88
IPA
0.78
2
33.27
35.23
IPA
-1.96
3
34.65
35.02
IPA
-0.37
average
34.19
34.71
-0.52
std. dev.
0.80
0.73
1.38
D 1
45.21
32.51
IPA
12.70
2
43.58
31.88
IPA
11.70
3
42.27
30.23
IPA
12.04
average
43.69
31.54
12.15
std. dev.
1.47
1.18
0.51
E 1
36.18
31.19
IPA
4.99
2
35.99
28.68
IPA
7.31
3
35.10
37.22
IPA
-2.12
average
35.76
32.36
3.39
std. dev.
0.58
4.39
4.91
f 1
32.88
13.881
IPA
19.00
2
30.13
29.19
IPA
0.94
3
27.91
23.82
IPA
4.09
average
30.31
22.30
8.01
std. dev.
2.49
7.77
9.65
G 1
33.85
29.96
IPA
3.90
2
39.42
30.72
IPA
8.70
3
39.98
33.34
IPA
6.63
average
37.75
31.34
6.41
std. dev.
3.39
1.78
2.41
H 1
38.78
32.84
IPA
5.94
2
39.28
33.29
IPA
5.99
3
38.90
33.61
IPA
5.29
average
38.99
33.25
5.74
std. dev.
0.26
0.39
0.39
J 1
45.56
24.93
IPA
20.63
2
44.90
24.00
IPA
20.90
3
47.52
26.45
IPA
21.07
average
45.99
25.12
20.87
std. dev.
1.36
1.24
0.22
1 Individual aliquots were 13.4 and 14.3 percent water.
B-8
-------
SD - Laundry Detergent
Lab
Number
Total
Water
Internal
VOC (%)
Volatiles !%)
Content (%)
Standard
A
1
2.94
1.23
IPA
1.71
2
3.07
1.24
I PA
1.82
3
3.34
1.36
I PA
1.98
average
3.12
1.28
1.84
std. dev.
0.20
0.07
0.14
B
1
1.85
2.62
I PA
-0.77
2
1.40
3.06
I PA
-1.66
3
1.37
3.10
I PA
-1.73
average
1.54
2.93
-1.39
std, dev.
0.27
0.27
0.54
D
1
1.35
1.67
IPA
-0.32
2
1.39
1.73
IPA
-0.34
3
1.19
1.55
IPA
-0.36
average
1.31
1.65
-0.34
std. dev.
0.11
0.09
0.02
E
1
0.59
2.24
IPA
-1.65
2
0.48
2.94
IPA
-2.46
3
0.50
2.55
IPA
-2.05
average
0.52
2.58
-2.05
std. dev.
0.06
0.35
0.41
F
1
0.87
1.28
IPA
-0.41
2
0.99
1.06
IPA
-0.07
3
1.26
1.51
IPA
-0.25
average
1.04
1.28
0.24
std, dev.
0.20
0.23
0.17
G
1
1.85
water was not detected
2
2.12
3
1.51
average
1.83
std. dev.
0.31
H
1
2.77
water detected below analytical
2
2.18
detection
limit - no analysis
3
2.53
performed
average
2.49
std. dev.
0.30
J
1
1.19
1.82
IPA
-0.62
2
2.47
2.20
IPA
0.27
3
1.28
2.22
IBA
-0.94
average
1.65
2.08
-0,43
std. dev.
0.71
0.23
0.63
B-9
-------
A A - Furniture Polish
Lab Number
Total
Water
Internal
VOC (%)
Volatiles {%)
Content (%}
Standard
A 1
95.80
73.69
I PA
22.10
2
95.72
68.92
I PA
26.79
3
95.62
70.05
I PA
25.57
average
95.71
70.89
24.82
std. dev.
0.09
2.49
2.43
B 1
94.93
80.21
I PA
14.72
2
95.96
75.74
I PA
20.22
3
96.31
72.71
I PA
23.60
average
95.73
76.22
19.51
std. dev.
0.72
3.77
4.48
D 1
95.56
73.43
iPA
22.13
2
95.80
79.13
IBA
16.67
3
95.39
79.53
IPA
15.86
average
95.59
77.36
18.22
std. dev.
0.20
3.41
3.41
E 1
83.42
66.58
IPA
16.85
2
84.40
67.24
IPA
17.16
3
83.75
66.86
IPA
16.89
average
83.86
66.89
16.97
std. dev.
0.50
0.33
0.17
F 1
98.14
84.16
IPA
13.98
2
94.59
63.95
IPA
30.64
3
93.64
74.62
IPA
19.02
average
95.46
74.24
21.21
std. dev.
2.37
10.11
8.54
G 1
96.65
66.74
IPA
29.91
2
97.63
75.74
IPA
21.90
3
96.30
75.05
IPA
21.26
average
96.86
72.51
24.36
std. dev.
0.69
5.01
4.82
H 1
95.46
71.46
IPA
24.00
2
95.78
74.26
IPA
21.52
3
95.52
73.01
IPA
22.51
average
95.59
72.91
22.68
std. dev.
0.17
1.40
1.25
J 1
96.11
68.90
IBA
27.22
2
93.75
68.09
IPA
25.66
3
96.19
73.40
IPA
22.80
average
95.35
70.13
25.22
std, dev.
1.39
2.86
2.24
B-10
-------
AB - Aerosol Hairspray
Lab Number
Total
Water
Internal
VOC (%)
Volatiles {%)
Content {%)
Standard
A 1
96.25
17.79
IPA
78.45
2
96.27
17.15
IPA
79.12
3
96.08
17.52
IPA
78.56
average
96.20
17.49
78.71
std, dev.
0.10
0.32
0.36
B 1
95.86
17.13
[PA
78.73
2
95.68
16.82
IPA
78.86
3
95.87
17.04
IPA
78.83
average
95.80
17.00
78.81
std. dev.
0.11
0.16
0.07
D 1
94.30
20.35
IBA
79.35
2
94.74
23.62
IPA
71.12
3
94.05
25.83
IPA
68.22
average
94.36
23.27
72.90
std. dev.
0.35
2.76
5.77
E 1
95.27
20.79
IPA
74.49
2
95.54
22.66
IPA
72.88
3
95.98
21.46
IPA
74.52
average
95.60
21.64
73.96
std. dev.
0.36
0.94
0.94
F 1
94.40
19.08
IPA
75.32
2
95.06
17.63
IPA
77.43
3
94.47
20.31
IPA
74.16
average
94.64
19.01
75.64
std. dev.
0.36
1.34
1.66
G 1
95.66
12.20
IPA
83.46
2
96.74
12.44
IPA
84.30
3
96.53
14.04
IPA
82.49
average
96.31
12.89
83.42
std. dev.
0.57
1.00
0.90
H 1
95.88
15.38
IPA
80.50
2
96.44
16.39
IPA
80.05
3
95.46
16.63
IPA
78.83
average
95.93
16.13
79.79
std. dev.
0.49
0.66
0.86
J 1
96.03
16.56
IPA
79.47
2
95.53
16.96
IPA
78.57
3
95.65
10.74
IPA
84.91
average
95.74
14.75
80.98
std. dev.
0.26
3.48
3.43
B-11
-------
AC - Aerosol Deodorant
Lab Number
Total
Water
Internal
VOC{%)
Volatiles (%
Content {%!
Standard
A 1
99.88
5.65
I PA
94.23
2
99.95
5.58
IBA
94.37
3
99.95
5.75
I PA
94.21
average
99.93
5.66
94.27
std. dev.
0.04
0.09
0.09
B 1
99.61
6.58
I PA
93,03
2
99.47
6.42
I PA
93.05
3
99.66
6.85
I PA
92.81
average
99.58
6.61
92.96
std. dev.
0.10
0.21
0.13
D 1
99.87
6.44
I PA
93.43
2
99.90
6.22
I PA
93.68
3
99.72
6.85
I PA
92.87
average
99.83
6.50
93.33
std, dev.
0.10
0.32
0.41
E 1
99.76
6.54
I PA
93.22
2
99.40
6.96
I PA
92.40
3
99.51
7.40
fPA
92.11
average
99.56
6.97
92.58
std. dev.
0.18
0.43
0.58
F 1
99.61
4.81
IBA
94.80
2
99.72
5.59
I PA
94.13
3
100.00
5.01
IPA
94.99
average
99.78
5.14
94.64
std. dev.
0.20
0.40
0.45
G 1
100.75
5.46
I PA
94.54
2
100.70
6.29
IPA
93.71
3
100.67
5.65
IPA
94.35
average
100.71
5.80
94.20
std, dev.
0.04
0.43
0.43
H 1
99.83
5.38
IPA
94.45
2
99.88
5.52
IPA
94.36
3
99.72
5.40
IPA
94.32
average
99.81
5.43
94.38
std. dev.
0.08
0.08
0.07
J 1
100.14
5.54
IPA
94.60
2
99.65
5.89
IPA
93.76
3
99,84
5.95
IPA
93.90
average
99.88
5.79
94.09
std. dev.
0.25
0.22
0.45
B-12
-------
AD - Glass Cleaner
Lab Number
Total
Water
Internal
VOC (%}
Volatiles (%)
Content {%}
Standard
A 1
99.50
93.83
IBA
5.67
2
99.53
90.64
IBA
8.89
3
99.50
93.24
IBA
6.27
average
99.51
92.57
6.94
std. dev.
0.02
1,70
1.71
B 1
99.34
81.21
IBA
18.13
2
99.27
93.56
IBA
5.71
3
99.53
95.69
IBA
3.84
average
99.38
90.15
9.23
std. dev.
0.13
7.82
7.77
D 1
99.49
99.88
IBA
-0.39
2
99.60
96.63
IBA
2.97
3
99.54
95.03
IBA
4.51
average
99.54
97.18
2.36
std. dev.
0.05
2.47
2.51
E 1
99.44
96.15
IBA
3.29
2
99.54
102.62
IBA
-3.08
3
99.50
103.73
IBA
-4.23
average
99.49
100.83
-1.34
std. dev.
0.05
4.09
4.05
F 1
99.41
94.69
IBA
4.72
2
99.55
93.74
IBA
5.81
3
99.84
93.34
IBA
6.50
average
99.60
93.92
5.68
std. dev.
0.22
0.69
0.90
G 1
99.83
83.67
IPA
16.16
2
99.98
80.26
IPA
19.72
3
99.95
84.00
IPA
15.95
average
99.92
82.64
17.28
std. dev.
0.08
2.07
2.12
H 1
99.46
88.99
IBA
7.88
2
99.82
82.48
IPA
17.34
3
99.38
99.96
IBA
9.42
average
99.55
90.48
11.55
std. dev.
0.23
8.84
5.08
J 1
99.55
79.96
IPA
19.59
2
99.92
86.85
IBA
13.07
3
100.28
86.35
IBA
13.94
average
99.92
84.39
15.53
std. dev.
0.37
3.84
3.54
B-13
-------
FA - Carpet Cleaner
Lab Number
Total
Water
Internal
VOC (%)
Volatiles (%)
Content (%)
Standard
A 1
98.73
42.11
I PA
56.62
2
98.58
71.13
I PA
27.46
3
98.60
63.46
I PA
35.14
average
98.64
58.90
39.74
std. dev.
0.08
15.04
15.11
B 1
98.91
37.99
I PA
60.92
2
97.97
46.81
I PA
52.16
3
98.80
42.08
I PA
56.72
average
98.56
42.29
56.60
std. dev.
0.51
4.42
4.38
D 1
98.25
78.65
I PA
19.60
2
98.18
83.13
I PA
15.05
3
97.67
81.71
I PA
15.96
average
98.03
81.16
16.87
std. dev.
0.31
2.29
2.41
E 1
97.29
78.86
I PA
18.43
2
97.67
79.06
I PA
18.61
3
97.15
87.00
I PA
10.15
average
97.37
81.64
15.73
std. dev.
0.27
4.64
4.83
F 1
98.69
36.66
I PA
62.03
2
97.71
57.79
IPA
39.92
3
97.56
62.31
IPA
35.25
average
97.99
52.26
45.73
std. dev.
0.61
13.69
14.31
G 1
98.63
72.54
IPA
26,09
2
99.71
71.79
IPA
27.91
3
99.60
77.96
IPA
21.64
average
99.31
74.10
25.21
std. dev.
0.59
3.37
3.23
H 1
98.32
82.67
IPA
15.65
2
96.62
78.52
IPA
18.10
3
97.30
81.30
IPA
16.00
average
97.41
80.83
16.58
std, dev.
0.86
2.11
1.33
J 1
99.74
27.54
IPA
72.20
2
99.23
24.64
IPA
74.59
3
99.38
14.61
IPA
84.77
average
99.45
22.26
77.19
std. dev.
0.26
6.78
6.67
B-14
-------
FB - Tire Cleaner
Lab Number
Total
Water
Internal
VOC(%)
Volatiles (%)
Content (%}
Standard
A 1
76.63
60.83
I PA
15.80
2
76.96
62.58
I PA
14.37
3
77.01
61.85
I PA
15.16
average
76.87
61.75
15.11
std. dev.
0.21
0.88
0.72
B 1
70.04
61.40
I PA
8.64
2
66.14
61.87
I PA
4.27
3
71.26
63.23
I PA
8.03
average
69.15
62.17
6.98
std. dev.
2.67
0.95
2.37
D 1
75.16
66.55
IBA
8.61
2
75.36
64.91
IPA
10.45
3
75.65
65.38
I PA
10.27
average
75.39
65.61
9.78
std, dev.
0.25
0.84
1.01
E 1
37.12
58.65
IPA
-21.53
2
55.19
61.65
IPA
-6.46
3
40.59
62.71
IPA
-22.12
average
44.30
61.00
-16.70
std. dev.
9.59
2.11
8.87
F 1
69.03
59.52
IPA
9.51
2
66.43
60.27
IPA
6.16
3
66.11
66.76
IPA
-0.65
average
67.19
62.18
5.01
std. dev.
1.60
3.98
5.18
G 1
71.43
64.19
IPA
7.24
2
72.26
67.36
IPA
4.89
3
69.87
64.06
IPA
5.82
average
71.19
65.20
5.98
std. dev.
1.21
1.87
1.18
H 1
72.80
65.38
IPA
7.42
2
72.84
65.08
IPA
7.76
3
73.34
64.13
IPA
9.21
average
72.99
64.86
8.13
std. dev.
0.30
0.65
0.95
J 1
73.00
60.66
IPA
12.34
2
74.11
59.31
IPA
14.80
3
69.83
61.54
IPA
8.28
average
72.31
60.51
11.81
std. dev.
2.22
1.12
3.29
B-15
-------
FC - Wall Cleaner
Lab Number
Total
Water
Internal
VOC{%)
Volatiles (%)
Content (%)
Standard
A 1
98.01
86.11
I PA
11.90
2
98.32
93.73
I PA
4.59
3
98.21
87.15
I PA
11.05
average
98.18
89.00
9.18
std. dev.
0.16
4.13
4.00
B 1
97,48
94.39
I PA
3.09
2
97.58
94.36
I PA
3.22
3
97.76
95.45
I PA
2.31
average
97.61
94.73
2.87
std. dev.
0.14
0.62
0.49
D 1
97.84
94.05
IBA
3.79
2
97.76
93.26
I PA
4.50
3
97.72
93.89
I PA
3.83
average
97.77
93.73
4.04
std. dev.
0.06
0.42
0,40
E 1
97.60
95.82
I PA
1.78
2
97.69
97.69
I PA
0.00
3
97.66
95.81
I PA
1.84
average
97.65
96.44
1.21
std. dev.
0.05
1.08
1.05
F 1
97.66
96.45
I PA
1.21
2
97.77
93.22
I PA
4.55
3
97.88
93.44
I PA
4.44
average
97.77
94.37
3.40
std. dev.
0.11
1.80
1.90
G 1
99.00
89.62
I PA
9.38
2
98.66
90.79
I PA
7.87
3
99.20
89.66
I PA
9.54
average
98.95
90.02
8.93
std. dev.
0.27
0.67
0.92
H 1
97.92
89.86
I PA
8.06
2
97.37
89.10
I PA
8.27
3
97.90
87.06
I PA
10.84
average
97.73
88.67
9.06
std. dev.
0.31
1.45
1.55
J 1
97.57
94.80
I PA
2.76
2
97.43
93.19
IPA
4.24
3
97.47
95.11
IPA
2.36
average
97.49
94.37
3.12
std. dev.
0.07
1.03
0.99
B-16
-------
FD - Engine Cleaner
Lab Number
Total
Water
Internal
VQC(%)
Volatiles (%)
Content (%S
Standard
A 1
94.17
69.42
I PA
24.74
2
94.13
71.90
I PA
22.24
3
94.05
70.14
I PA
23.91
average
94.12
70,49
23.63
std, dev.
0.06
1.28
1.27
B 1
92.79
70.57
I PA
22.22
2
92.65
71.49
I PA
21.16
3
93.29
70.97
I PA
22.32
average
92.91
71.01
21.90
std. dev.
0.34
0.46
0.64
D 1
93.57
62.34
IPA
31.23
2
93.30
77.48
IBA
15.82
3
93.10
74.80
IPA
18.30
average
93.32
71.54
21.78
std. dev.
0.23
8.08
8.27
E 1
93.59
68.40
IPA
25.19
2
93.14
70.29
IPA
22.85
3
93.11
69.89
IPA
23.22
average
93.28
69.53
23.75
std. dev.
0.27
0.99
1.26
F 1
93.82
68.66
IBA
25.16
2
92.23
71.73
IPA
20.50
3
92.47
68.88
IPA
23.59
average
92.84
69.75
23.08
std. dev.
0.86
1.71
2.37
G 1
93.94
72.52
IPA
22.01
2
94.00
71.04
IPA
22.96
3
94.54
68.44
IPA
26.09
average
94.16
70.67
23.69
std. dev.
0.33
2.06
2.14
H 1
93.10
72.90
IPA
20.20
2
93.14
71.33
IPA
21.81
3
93.36
71.43
IPA
21,93
average.
93.20
71.89
21.31
std. dev.
0.14
0.88
0.97
J 1
93.93
68.83
IPA
25.10
2
93.38
65.86
IPA
27.52
3
93.10
72.78
IPA
20.32
average
93.47
69.16
24.31
std. dev.
0.42
3.48
3.67
B-17
-------
APPENDIX C
LABORATORY RESULTS1 USING NORMALIZED IPA/IBA RATIO FOR PRODUCTS
CONTAINING 2-PROPANOL
1 Laboratory codes were randomly assigned and do not reflect the order in
Table 3-2. Although the code letter used by each laboratory is not revealed in this
report, the same code letter was used to refer to a given laboratory throughout the
study and this report.
C-1
-------
LP - Liquid Glass Cleaner
Lab Number
Total
Water
Internal
VOC{%}
Volatiles (%) Content 1%)
Standard
A 1
99.83
91.10
IBA
8.73
2
99.84
91.14
IBA
8.70
3
99.81
91.14
IBA
8.67
average
99.83
91.13
8.70
std. dev.
0.02
0.02
0.03
B 1
99.90
93.55
I PA
6.35
2
99.82
93.35
IBA
6.47
3
99.85
93.27
IBA
6.58
average
99.86
93.39
6.47
std. dev.
0.04
0.14
0.11
D 1
99.77
89.58
IBA
10.19
2
99.81
94.23
IBA
5.58
3
99.87
92.06
IBA
7.81
average
99.82
91.96
7.86
std. dev.
0.05
2.33
2.31
E 1
99.87
93.86
IBA
6.01
2
99.86
93.61
IBA
6.22
3
99.83
90.15
IBA
9.68
average
99.85
92.54
7.30
std. dev.
0.02
2.07
2.06
F 1
99,92
94.41
IBA
5.51
2
99.86
91.71
IBA
8.15
3
99.84
93.53
IBA
6.31
average
99.87
93.22
6.66
std. dev.
0.04
1.38
1.35
G 1
99.85
92.09
IBA
7.76
2
99.88
90.75
IBA
9.13
3
99.85
90.95
IBA
8.90
average
99.86
91.26
8.59
std. dev.
0.02
0.72
0.73
H 1
99.82
92.73
IBA
7.09
2
99.89
93.52
IBA
6.37
3
99.90
94.66
IBA
5.24
average
99.87
93.64
6.24
std. dev.
0.04
0.97
0.93
J 1
99.79
90.44
IBA
9.35
2
99.83
88.44
IBA
11.40
3
99.84
90.02
IBA
9.82
average
99.82
89.63
10.19
std. dev.
0.03
1.06
1.07
-------
AD - Glass Cleaner
Lab Number
Total
Water
Internal
VOC(%)
Volatiles (%)
Content {%)
Standard
A 1
99.50
93.83
IBA
5.67
2
99.53
90.64
IBA
8.89
3
99.50
93.24
IBA
6.27
average
99.51
92.57
6.94
std. dev.
0.02
1.70
1.71
B 1
99.34
81.21
IBA
18.13
2
99.27
93.56
IBA
5.71
3
99.53
95.69
IBA
3.84
average
99.38
90.15
9.23
std, dev.
0.13
7.82
7.77
D 1
99.49
99.88
IBA
0.39
2
99.60
96.63
IBA
2.97
3
99.54
95.03
IBA
4.51
average
99.54
97.18
2.36
std. dev.
0.05
2.47
2.51
E 1
99.44
96.15
IBA
3.29
2
99.54
102.62
IBA
-3.08
3
99.50
103.73
IBA
-4.23
average
99.49
100.83
-1.34
std. dev.
0.05
4.09
4.05
F 1
99.41
94.69
IBA
4.72
2
99.55
93.74
IBA
5.81
3
99.84
93.34
IBA
6.50
average
99.60
93.92
5.68
std. dev.
0.22
0.69
0.90
G 1
99.84
83.67
IPA
16.18
2
99.99
93.82
IBA
6.17
3
100.20
98.21
IBA
1.99
average
100.01
91.90
8.11
std. dev.
0.18
7.46
7.29
H 1
99.46
88.99
IBA
7.88
2
99.82
92.27
IBA
7.54
3
99.38
99.96
IBA
9.42
average
99.55
93.74
8.28
std. dev.
0.23
5.63
1.00
J 1
99.55
92.61
IBA
6.93
2
99.92
86.85
IBA
13.07
3
100.28
86.35
IBA
13.94
average
99.92
88.60
11.31
std. dev.
0.37
3.48
3.82
C-3
-------
APPENDIX D
PROTOCOL FOR INTERLABORATORY STUDY OF A TEST METHOD FOR
MEASURING TOTAL VOLATILE ORGANIC COMPOUND CONTENT OF CONSUMER
PRODUCTS
Interlaboratory Study Coordinator
The Interlaboratory Study (ILS) coordinator at RTI is Gary Howe, telephone
(91 9J-541-1228, fax (91 9)-541-5929, Internet gbh@rti.org. Contact him
whenever questions arise concerning any aspect of the ILS. The coordinator should
be contacted especially if an error in sample analysis occurs, to enable a decision
concerning whether a new set of samples will be provided. R.K.M. Jayanty,
telephone (919)-541-6483 will also be available to answer questions.
Test Method Version
Use the version of the method ("Determination of Volatile Organic
Compounds in Consumer Products", Attachment A1) provided with the test
samples. Do not use the earlier version included with the proposal request.
Number of Samples
Each laboratory will analyze four product samples from each of four
categories (solids and gels, liquids, aerosols, and foams). As specified in the test
method, measurement of total VOC content requires two aliquots for total volatile
content determination and two aliquots for water content determination. Subtract
the averages of these determinations to produce one test result of total VOC
content for each product.
Number of Replicates
Each laboratory will perform triplicate analyses on each sample. RTI has
provided a single sample of each product with sufficient quantity for triplicate
analyses. A summary of the number of products and replicates is shown in Table
1, below.
1 A revised version of the method, referred to in this protocol as Attachment A, is provided as
Appendix A of this report,
D - 1
-------
Table 1. Sample Analysis Matrix
Product Category
Number of
Products
Number of
Replicates3
Number of
Aliquotsb
Solids and gels
4
12
48
Liquids
4
12
48
Aerosols
4
12
48
Foams
4
12
48
Total
16
48
192
a The method will be used three times for analysis of each product.
b Four aliquots of each replicate are needed, two for total volatile content
determination and two for water content determination.
Order of Analyses
For the purposes of this interlaboratory study, it is important that the
analyses be run in the correct sequence. Rules for the order of analyses are given
below:
1) Complete one entire VOC analysis (i.e., both the total volatile content
analysis and the water content analysis) before starting the next VOC
analysis of the same product.
2} Groups of different products may be analyzed in one batch, but it is
essential that the replicate analyses for a given product be performed on
different days. This ensures that between day variability is reflected in the
study's estimate of precision.
3) Collect both paired aliquots for a given analysis within a few minutes of
each other.
4) Both paired aliquots should be analyzed in the same batch (i.e., in the
same oven batch, or within the same day by gc).
5) Use one person and one set of test apparatus for any particular step in the
test method. This combination of operator and apparatus should be
maintained throughout the study for testing of all products.
D - 2
-------
If you are unclear about the order of analysis, please call the ILS coordinator before
starting sampling. An example, showing order of analysis for a single product is
given below.
Example; Analysis of windshield washer fluid
Pay 1
Take two aliquots and measure the total volatile content. Average the results.
Take two aliquots and measure the water content. Average the results. Subtract
the average water content from the average total volatile content. This provides
one result of total VOC content.
Day 2
Repeat the Day 1 scheme.
Dav 3
Repeat the Day 2 scheme.
Reporting Requirements
Send completed data sheets for all analyses as soon as testing is completed.
Results must be sent within one month after receipt of samples. Data sheets are
provided as Attachment B2; examples of completed data sheets are provided as
Attachment C3. Please return results to:
Gary Howe
Research Triangle Institute
Building 7
PO Box 12194
Research Triangle Park, NC 27709-2194
Each participating laboratory is also asked to provide information (on the form
provided) concerning specific facilities and equipment used for analysis of test
samples. In addition, a log of any special events that arise during testing should be
maintained and submitted to the ILS coordinator with the test results at the
completion of testing.
2 The data forms, referred to in this protocol as Attachment B, are Included in Appendix A of this
report.
3 The examples of completed data forms, referred to as Attachment C in the protocol, are not
included in this report.
D - 3
-------
Materials Furnished
Participating laboratories are expected to provide all apparatus and materials as
described in the method, except the aerosol sampling assembly and the double
ended syringe needles (VACUTAINER needles) described in Appendix A, Section
2.1.9. The sampling assembly and fifty needles are included with the samples.
Please use a new needle for each product; the same needle can be used for both
aliquots of the same product. A short length of TYGON tubing is included for use
with narrow diameter aerosol valve stems. The tubing should be cut and used as a
gasket between the sampling adapter and the product valve stem. The length of
tubing should be long enough to fit inside the Alitech adapter, but not so long as to
prevent depressing the valve stem (approximately 1/8 inch seems to work well).
D - 4
------- |