United States EPA Document# 740-S1-7002
Environmental Protection
Agency Office of Chemical Safety and Pollution Prevention
Indoor Exposure Product Testing Protocols
Version 2.0
2017
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Table of Contents
Introduction 1
Contextualizing Information for Product Use 4
1. Exposure Testing Protocol 1: Source Characterization 6
2. Exposure Testing Protocol 2: Emission from Water to Air 11
3. Exposure Testing Protocol 3: Short-Term Emission Testing 25
4. Exposure Testing Protocol 4: Long-Term Emission Testing - Partition and Diffusion
Coefficients 40
5. Exposure Testing Protocol 5: Particulate Matter Formation Due to Mechanical
Forces Applied to Product or Article Surfaces 47
6. Exposure Testing Protocol 6: Transfer of Chemicals from Source to Settled Dust 56
7. Exposure Testing Protocol 7: Photolysis under Simulated Indoor Lighting Conditions 64
8. Exposure Testing Protocol: Migration to Saliva (Oral Exposure) 71
9. Exposure Testing Protocol 9: Migration to Sweat (Dermal Exposure) 77
10. Exposure Testing Protocol 10: Migration of chemical from solid material to water 84
Tables
Table 1. Indoor Exposure Testing Protocols Names and Metrics 2
Table 2. Test Matrix for Emissions from Water or Aqueous Solutions to Indoor Air 16
Table 3. Commonly used environmental chambers for testing of chemical emissions from products and
articles 25
Table 4. An example of test matrix and temperature settings for micro chamber tests 37
Table 5. Methods for experimental determination of partition and diffusion coefficients 40
Table 6. Experimental schedule for Transfer of Chemicals from Source to Settled Dust 57
Table 7. Operating conditions of small test chambers for testing migration of chemical of
interest from source article to dust 58
Table 8. Example Experimental Schedule for Migration into Water: Liquid to Solid Ratio 85
Table 9. EPA Analytical Methods for Various Chemicals 87
Table 10. Example Experimental Schedule for Migration Rate into Water over Time 102
Table 11. Sample Collection Schedule for Migration Rate into Water over Time 104
Figures
Figure 1. Conceptual Diagram of protocols overlaid with source-to-dose continuum for
consumer products and articles 3
Figure 2. Experimental Set up for Determination of overall mass transfer coefficient for still water or
aqueous solution 11
Figure 3.. Experimental Set up for Determination of overall mass transfer coefficient for
agitated water or aqueous solution 12
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Figure 4.0verall liquid phase mass transfer coefficient versus 1/T(K) Data points are
hypothetical 18
Figure 5. Schematic of example 30 m3 full-scale chamber (Liu et al., 2012) 25
Figure 6.. Schematic diagram of small-scale VOC emission chamber (Yerramilli et al., 2010) 26
Figure 7. Schematic plot of Field and Laboratory Emission Cell (FLEC) (Kim et al., 2007) 26
Figure 8.. Photo of micro-chamber/thermal extractor (i-iCTE) from Markes International,
Llantrisant, UK (Cleanroom Technology, 2011) 26
Figure 9. An example of a micro chamber system. Note that the Polyurethane Foam (PUF)
air samplers are directly connected to the chamber air outlet 33
Figure 10.. An example of area-specific emission rate (E) as a function of temperature based
on data from micro chamber tests 34
Figure 11.. An example of the relationship between the inlet air flow rate and air pressure at
the gas tank regulator. Note that the calibration curves at different temperatures
may be slightly different 36
Figure 12.. Schematic plot of the microbalance test system (Cox et al., 2001) 39
Figure 13.. Schematic plot of the dynamic-static chamber (He et al., 2010) 40
Figure 14.. Schematic plot of the diffusion metric method (Bodalal et al., 2001) 40
Figure 15.. Schematic plot of the dual-chamber method (Xiong et al., 2009) 41
Figure 16. Schematic plot of the dual chamber method (Liu et al., 2014) 42
Figure 17. Schematic plot of the cup method (Blondeau et al., 2003) 42
Figure 18. Schematic of the test facility for particle generation due to abrasion 46
Figure 19. Expected particle count profile during an abrasion test. The data collected after
the abraser stops is used to estimate the deposition rate constant 52
Figure 20. Semi-log plot for particle count versus time during the decay phase (i.e. flushing
the chamber) 53
Figure 21. Collecting dust from test panels by placing the panel on the 4-mil-thick aluminum
foil vertically (left) and then tilt it further towards the dust-laden side to form an
approximately 80ฐ angle with the aluminum foil. Use the spatula rod to tap the back
of the panel in both positions 60
Figure 22.The dust particles form a line after the aluminum sheet is folded into the U shape.
The unfolded panel shown in this picture is a thin aluminum plate instead of 4-mil
aluminum foil 60
Figure 23. Dust sample is transferred from folded aluminum sheet to the scintillation vial 60
Figure 24. Graphic example of generic procedure for photolysis without dust 66
Figure 25. Graphic example of generic procedure for photolysis with dust 67
Figure 26. Graphic example of procedure for analyzing migraiton from product or article surface to
saliva 73
Figure 27. Graphic example of small-scale procedure for analyzing migration from product or article
surface to sweat 80
Figure 28. Diagram of Relationships between Components in Leaching Protocol 83
Figure 29. Retsch cryomill uses liquid Nitrogen to embrittle polymer samples 91
Figure 30. Retsch Jet Sieve for Generating Particles of Discrete Size 91
Figure 31. Micromeritics Gemini V Series BET Surface Area Analyzer 92
Figure 32. General Migration Rate into Water Test Apparatus 93
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CONTRIBUTORS and ACKNOWLEDGEMENTS
This report was developed by the United States Environmental Protection Agency (US EPA),
Office of Chemical Safety and Pollution Prevention (OCSPP), Office of Pollution Prevention and
Toxics (OPPT).
Acknowledgements
This document was developed by EPA scientists in the Risk Assessment Division of the Office of
Pollution Prevention and Toxics and the National Risk Management Research Laboratory of the
Office of Research and Development. The document was reviewed by scientists from EPA's
Office of Pesticide Programs, Office of Research and Development, and the Consumer Product
Safety Commission. This document was developed with support from ICF International under
EPA Contract # EP-W-12-010.
Disclaimer
Mention of trade names of commercial products should not be interpreted as an endorsement
by the U.S. Environmental Protection Agency.
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Introduction
EPA's Office of Pollution Prevention and Toxics (OPPT) has developed a set of ten indoor exposure
testing protocols intended to provide information on the purpose of the testing, general description of
the sampling and analytical procedures, and references for tests that will be used to inform and refine
estimates of indoor exposures. The scope of these protocols is limited to testing chemicals in consumer
products and articles, including building materials, used in indoor environments. These protocols are
intended to address the potential for these chemicals to migrate to indoor exposure media such as air or
dust, where exposure may occur.
These protocols are general in nature and will need to be tailored to the specific type of chemical to be
analyzed, the particular product or article which is being evaluated, and the data quality objective for
the testing. The word "should" is used throughout this document. Each protocol has a modifications
section. During modifications, the organization performing testing is expected to revise the generic
indoor exposure testing protocol replacing "should" with language such as "shall" "will" or "must." Most
protocols were developed based on existing standard test methods. In the absence of standard
methods, the most commonly used methods found in the literature were used.
Multiple protocols may be used to evaluate potential exposures when using products and articles in
indoor environments. For example, if the testing objective is to evaluate how much of a particular
chemical is emitted during a short-term use of a particular product indoors, the source characterization
protocol and the short-term emission test protocol would be appropriate. The protocols would be
modified to include the appropriate analytical method for the chemical of interest, the appropriate type
of chamber, sample preparation, sampling method, sampling volume, etc.
All of the indoor exposure testing protocols are designed to refine and improve exposure estimates.
Experimental results can be used, in combination with other information, to estimate environmental
concentrations and doses for human receptors. Lack of experimental data does not prevent estimation
of exposure as available exposure models can be used. However, models and estimation approaches
that use chemical and scenario specific experimental data rather than generic defaults can provide more
refined estimates of exposure. Refined estimates of exposure may be higher or lower than estimates
based on generic defaults.
The protocols should be modified using methodologies generally accepted in the relevant scientific
community at the time the study is initiated. Before starting to conduct any study that will use a
modified version of these protocols, a written test protocol is generally submitted to the Agency for
review. The following will be evaluated during the Agency review of the modified protocol:
a. data quality objective(s),
b. the sampling process design (experimental design),
c. sampling and analytical methods,
d. sample handling and custody,
e. quality control procedures and activities (including reference samples, duplicates, replicates,
etc.),
f. instruments and equipment to be used in conducting the testing,
g. data review, verification, and validation, and
h. reporting requirements.
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Additional information on the Agency's Quality Analysis procedures and programs is available (EPA,
2016). The final report should contain study results and sufficient contextualizing information on testing
conditions and analytical approaches to inform study results.
Each study should be conducted in good faith, with due care, and in a scientifically valid manner. The
protocols are listed below; they may be updated over time:
Table 1. Indoor Exposure Testing Protocols Names and Metrics
#
Name
Metrics (Units)
Chemical concentration or Weight fraction in
1
Source Characterization
product or article (ppm, fraction)
2
Emission from Water and Aqueous Sources to
Indoor Air (overall liquid-phase mass transfer
coefficient)
Liquid-phase, gas-phase, and overall mass transfer
coefficients KL, KG, K0l (m/h)
3
Short-Term Emission Testing
Emission rate (mg/hour)
Emission factor (mg/m2/hour)
4
Long-Term Emission Testing - Partition and
Diffusion Coefficients
Solid-phase diffusion coefficient (m2/h)
Material-air partition coefficient (dimensionless)
Gas-phase mass transfer coefficient (m/h)
5
Particulate Matter Formation Due to Mechanical
Forces Applied to Product or Article Surfaces
Particle generation rate (mg/hour)
L~
Migration to Dust (Transfer of Chemicals from
Time averaged air, wipe, or dust concentrations
O
Source to Settled Dust by Direct Contact)
(Hg/m3, |ig/m2, M-g/kg)
7
Photolysis under Simulated Indoor Lighting
Conditions
Time averaged air, wipe, or dust concentrations
(Hg/m3, |ig/m2, ug/kg)
Migration Rate into Saliva
8
Migration to Saliva (Oral Exposure)
(mg/cm2/hour)
Film Thickness (cm)
9
Migration to Skin (Dermal Exposure)
Loading (ng/cm2)
10
Migration of Chemical from Solid Material to
Water
Concentration in water (ng/L)
Emission rate (mg/hour)
Figure 1 provides an illustration of the types of potential exposures associated with the source (product
or article in the indoor environment), and how the exposure data produced from applying the test
protocols will be used to inform the potential for exposure. As shown in Figure 1, all of the indoor
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exposure protocols are designed for the purpose of informing potential exposures to human receptors.
The outputs of the protocols can be used along with other information such as receptor and
environment specific exposure factors to estimate dose. However, documentation of these pathways
and equations is beyond the scope of this document.
Short-Term Emissions to
Air
Long-Term Emissions to
Air
_ Emissions from Water to
Air
Photolysis
Particulate Matter
Formation
Migration to Dust
Migration and
Transport of
Chemical to Gas-
Phase Air,
Suspended Particles,
or Settled Dust
Legend
f Chemical Substance
1 Protocols
Source
Emissions and
Migration
Dose for
Receptor
Oral and
Inhalation
Dose from
Intake of
Dust and
Indoor Air
Migration to Saliva
Migration to Sweat
Migration to Water
Source Characterization
PRODUCT SOURCE
ARTICLE SOURCE
HUMAN RECEPTOR
Figure 1. Conceptual diagram of protocols overlaid with source-to-dose continuum for consumer products and
articles.
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Contextualizing Information for Product Use
Purpose and Description
For any indoor exposure testing protocol that is conducted, it is important to describe the context of the
testing with regard to potential exposures. Information on the conditions of use, potentially exposed
populations, properties and characteristics of the product or chemical, and other factors are needed to
better understand the relationship between the testing results and potential exposures. OPPT strongly
encourages provision of an introductory narrative that contains some or all of the following information:
1. A statement of the agreed upon objectives for product testing including what testing results and
contextualizing information will be provided.
2. A description that explains the combination of the product and/or article use category and
functional use category for the chemical substance.
3. Intended number and description of individuals (receptors) who use products (industrial
workers, commercial workers, high-frequency consumer use, low-frequency consumer use, use
by children, etc.).
4. Physical- chemical properties that govern the behavior of the chemical in the indoor
environment, including: Henry's Law constant, octanol-water partition coefficient, octanol-air
partition coefficient, material-air partition coefficient, water solubility, and vapor pressure.
Properties may need to be measured or adjusted for relevant indoor environment and/or body
temperatures reflecting conditions of use. Expected temperatures during use should be
reported.
5. Information characterizing the properties of the product. Properties of the consumer product
include density, physical form, method of application (spray, brush, roll-on), and whether
dilution occurs during routine use.
6. The typical setting for use (e.g., outdoors, indoors, residential, commercial).
7. Typical life expectancy of the article during use, typical or high-end mass of product used per
event, and duration of use per event.
The exposure potential of a chemical used in consumer products including articles is influenced by
several parameters. Chemicals that are part of formulated mixtures are generally liquids or semi-solids
and are used over time and disposed of. Chemicals that are added to articles or building materials are
generally part of solid matrices. The likelihood of a chemical migrating from an article is dependent on
the characteristics of the material of which the article is comprised as well as the chemical itself.
For example, polyurethane foam produced for specific purposes may have varying specifications for
properties, such as density, rigidity, and structure (closed vs. open cell), along with the thickness of the
product and its exposed surface area. These properties influence the likelihood of migration and are
thus important in understanding the potential for exposure. The overall impact of one or a combination
of these factors that could influence migration and exposure potential is not well characterized.
The objective of collecting this additional contextual information is to help refine exposure scenarios
and establish relationships back to source characterization as described in the protocol. Additional
contextual information, not described in the list above, may be required from the sponsor depending on
the specific chemical and product tested.
Reporting Requirements and Records Retention:
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There are many existing reporting templates for exposure and use information (OECD 2003;OECD 2016).
Use of existing templates may be helpful. OPPT strongly encourages additional exposure and use
information provided to be linked with product testing information through a narrative.
Records maintained and submitted to the EPA should include, but are not limited to, the following:
a. The original reference upon which information is based.
b. Identification and characterization of the test substance as provided by Sponsor.
c. Identification and characterization of the material in question.
d. Description of methods employed.
Any changes to exposure information provided within the introduction of test protocol reports shouldbe
documented. If it is necessary to make corrections or additions to the final report after it has been
accepted, such changes should be made in the form of an amendment issued by the Study Director. The
amendment should clearly identify the part of the study that is being amended and the reasons for the
alteration. Amendments should be signed and dated by the Study Director and Laboratory Quality
Assurance Officer.
References
U.S. EPA (2016). How EPA Manages the Quality of its Environmental Data, https://www.epa.gov/aualitv
OECD (2003). Guidance Document on Reporting Summary Information on Environmental Occupational
and Consumer Exposure. ENV/JM/MONO(2003)16
OECD (2016). OECD Harmonised Templates 301 to 306: Use and Exposure Information.
https://www.oecd.org/ehs/templates/harmonised-templates-use-exposure-information.htm
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1. Source Characterization
1.1. Purpose:
The objective of this protocol is to determine the concentration (mg/kg, with at least three significant
figures) of the chemicals of interest present within the consumer product or article.
1.2. Modifications:
This protocol is general, and it is anticipated that during protocol development and finalization,
additional modifications will be made to tailor the sampling parameters or analytical techniques to the
specific chemical and product tested, as well as to Agency recommendations specific to particular
products, chemicals, or exposure scenarios of interest.
1.3. Description:
The methods described here are generally described in OCSPP test guidelines 830.1000 and 830.1550.
While these guidelines are tailored to pesticide formulations, considerations are similar for non-
pesticide product testing (EPA 1996) (EPA 1998). Additional information based on Cox et al. (2001) and
Guo et al. (2009) and Health Canada is provided for context. This protocol is organized around testing
protocols for liquid-based consumer products and testing of solid-articles.
The Sponsor should provide information regarding product or article formulation, including the state of
the chemical (e.g., as an additive or chemically bound to the substrate) and its functionality, method of
application, as well as a list of consumer articles containing said chemical(s).
The Sponsor should work with their processing customers to provide information characterizing the type
and properties of the consumer product or article itself. Properties of the consumer product or article
that should be reported, if applicable, include polymer identity, physical form, density, rigidity, porosity,
surface area, thickness, typical setting for consumer product use (outdoors, indoors, residential,
commercial), and typical life expectancy of article in consumer use (See Contextualizing Information for
Product Use section above).
1.4. Experii ;ign:
To determine the concentration of chemicals within a product or article, sample preparation and
analysis should be tailored to the chemical and the product or article properties. Following are example
methods of sample preparation for liquid and solid samples. The methods presented are generally
applicable to semi-volatile organic compound (SVOC) additives. More volatile additives, such as VOCs
used in spray-applied products, may require different sample preparation methods to prevent losses
and these steps should be documented.
1.4.1. Screening for the Chemicals of Interest
If the chemical of interest contains elements able to be analyzed through X-ray Fluorescence (XRF) or
otherwise detected via screening methods, these may be employed to show the presence or absence of
the chemical of interest prior to more detailed testing. If screening tests are not available or show the
potential presence of the chemical of interest, the sponsor should test for the concentration of that
chemical using one of the methods described in the following sections or another method appropriate
to the chemical and product or article combination.
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1.4.2. Preparation of Liquid Test Specimens for Consumer Products
This methodology (Guo et al., 2009) is recommended for consumer products that exist in a liquid state.
Samples should be prepared in duplicate.
Accurately weigh 1.5 mL of liquid sample into the sample vial and add recovery check standard
for checking the extraction efficiency.
Dilute each sample with 25 mL of appropriate solvent (e.g., dichloromethane, methanol, etc.)
Seal the vial, and sonicate the samples for 10 minutes.
Filter the diluted sample with a 50-mL tube-top filter with a 0.22-nm pore size.
Transfer 10 mL of the filtered liquid to a 10-mL volumetric flask with a 0.1-nm pore size syringe
filter to further remove high molecular weight polymers or other suspended particles that are
suspected to remain present.
Add the internal standard to each sample.
Cap the flask and sonicate the sample for 10 minutes.
Note that, if the extracts contain high concentrations of target chemicals, a serial dilution is needed to
reduce concentrations to within the calibration range and to prevent instrument contamination. Note
that, if spray-applied products are considered, modifications to preparation of sample may be required
and preparation and analysis methods should prevent loss of volatile components of interest. Other
examples of protocols that measure concentration of chemicals in liquid products are test methods from
Health Canada's Product Safety Laboratory (Health Canada 2014) (Health Canada 2015a)
1.4.3. Preparation of Solid Samples for Consumer Products Containing SVOC Additives
To analyze chemicals in solid articles that are applied to the surface of an article (e.g., PFC telomers or
polymers applied to fabrics) and articles that can be easily cut into fine, thin pieces (e.g., caulking
material), sample coupons can be used. For chemicals found within solid, polymeric articles, ground
samples or cut coupons can be created as described in this section. Wipe samples have been used to
measure chemicals available on the surface of an article for oral or dermal transfer but are not believed
to be accurate for measuring the concentration of a target chemical. As such, collection of wipe samples
is not recommended under this protocol.
If using coupons, sample coupons should be cut from the article and sonicated. Additional sample
preparation details for cut coupons are detailed in test methods from Health Canada's Product Safety
Laboratory and are summarized here. Cut samples into small 2-3 cm2 pieces, weigh 0.1 grams of sample,
add toluene or another appropriate solvent to a flask and secure with a stopper, shake the sample with
a wrist-action shaker at speed 4 for 1 hour, remove samples from the shaker and transfer to a
scintillation vial, take aliquots for extraction and analysis as detailed in the following section (Health
Canada 2015b). Additional details are also available in (Guo et al. 2009).
If using ground samples, two samples should be selected from the article. Article samples should be
ground in a cryogenic grinder, such as a Retsch CryoMill, to reduce the heterogeneity of test materials
and increase chemical recovery from the article. An article sample of the size appropriate to fill the
grinding jar approximately 1/3 full should be placed in a closed metal grinding jar that is continually
cooled with liquid nitrogen before and during the grinding process to maintain the temperature of -140
ฐC (Cox et al., 2001).
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After grinding, the desired size fraction of particles (less than 200 microns in diameter from each article)
should be obtained using an air jet sieving machine that is suitable for sieving low density materials,
which tend to agglomerate, to particle sizes in the low to sub millimeter size range. Use a spatula to
transfer the ground polymer into the scintillation vial.
After grinding, the appropriate size fraction of particle should be collected from the air jet sieving
machine in a fume hood with a low air speed. Avoid using strong air drafts; a gentle flow is needed to
prevent sample loss during collection.
The scintillation vials used for collecting samples should be stored in a desiccator for at least 8
hours.
Place a 30 cm by 30 cm sheet aluminum foil on the table of the fume hood.
Fold the aluminum foil to form a U shape; transfer the sample from the air sieve collector to
allow the particles to settle on the bottom of the U-shaped aluminum foil.
Place the folded aluminum sheet aside inside the fume hood; place a new piece of aluminum foil
(roughly 30 cm x 30 cm) on the table.
Place a centrifuge tube holder on the aluminum foil.
Place a 20-mL scintillation vial in the tube holder.
To transfer the ground polymer into the scintillation vial, tilt the folded aluminum foil to about
45ฐ to allow the ground materials to "flow" into the scintillation vial; tap gently with a spatula if
necessary (see Figure 23).
1.4.4. Analytical Methods for use with Sample Coupons or Ground Samples
Selection of the analytical methods for extracted samples depends on the properties of the chemicals of
interest and the type of sampling media. Instrumentation that may be utilized include, but is not limited
to liquid chromatography-mass spectrometry (LC-MS), gas chromatography-mass spectrometry (GC-
MS), liquid chromatography with tandem mass spectrometry (LC/MS/MS), gas chromatography with
tandem mass spectrometry (GC/MS/MS), or high performance liquid chromatography with tandem
mass spectrometry (HPLC-LC/MS/MS). For example, for Brominated Phthalate Flame Retardant and
decaBDE, chromatography or mass spectrometry in electron capture negative ionization mode (GC/MS-
ECNI) has been used (Stapleton et al., 2008).
1.5. Records Retention and Reporting of Results
1.5.1. Records to be Maintained
Records submitted to the EPA should include, but are not limited to, the following:
a. The original signed protocol and any amendments.
b. Identification and characterization of the test substance as provided by Sponsor.
c. Identification and characterization of the material in question.
d. Experiment initiation and termination dates.
e. Laboratory log books (e.g., stock solution concentration calculations and solution preparation,
calibration, and QC data).
f. Instrument (e.g., GC/ECNI) data files.
g. Spreadsheet files for data processing.
h. Chain of custody documentation, including sample storage and handling information.
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i. Copy of final report.
1.5.2. Final Report
A final report of the results of the study should be prepared and submitted to the EPA. The final report
should include, but is not limited to the following, when applicable:
a. Name and address of facility performing the study.
b. Dates on which the study was initiated and completed.
c. Objectives and procedures stated in the approved protocol, including any changes in the original
protocol.
d. Identification and characterization of the test substance as provided by sponsor.
e. A summary and analysis of the data and a statement of the conclusions drawn from the analysis.
f. A description of the transformations and calculations performed on the data.
g. A description of the methods used and reference to any standard method employed.
h. A description of the instrumentation utilized.
i. A description of the preparation of the test coupon, the test conditions, the testing
concentrations, and the duration of the test.
j. A description of sampling and analytical methods, including level of detection, level of
quantification, calibration information, and references.
k. A description of test specimens and test matrix.
I. A description of the test results including measured values for individual chemicals of interest
for each matrix.
m. A description of all circumstances that may affect the quality or integrity of the data.
n. The name of the study director, the names of other scientists or professionals, and the names of
all supervisory personnel involved in the study.
o. The signed and dated reports of each of the individual scientists or other professionals involved
in the study, if applicable.
p. The location where the raw data and final report are to be stored.
q. A statement prepared by the Quality Assurance Unit listing the types of inspections, the dates
that the study inspections were made, a description of the quality assurance and quality control
process, and the findings reported to the Study Director and Management.
r. A copy of all raw data including but not limited to instrumentation output, lab notebooks, and
data sheets, etc.
1.5.3. Changes to the Final Report
If it is necessary to make corrections or additions to the final report after it has been accepted, such
changes should be made in the form of an amendment issued by the Study Director. The amendment
should clearly identify the part of the study that is being amended and the reasons for the alteration.
Amendments should be signed and dated by the Study Director and Laboratory Quality Assurance
Officer.
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1.5.4. Changes to the Protocol
Planned changes to the protocol should be in the form of written amendments signed by the Study
Director and approved by the sponsor's representative and submitted to EPA using procedures in 40 CFR
790.50. Amendments should be considered as part of the protocol and should be attached to the final
protocol. Any other changes should be in the form of written deviations signed by the Study Director
and filed with the raw data. All changes to the protocol should be indicated in the final report. Changes
to the test standard require prior approval from EPA using procedures in 40 CFR 790.55.
1.6. References
EPA (1996). OCSPP Guideline 830.1550. Product Identity and Composition.
EPA (1998). OCSPP Guideline 830.1000. Background for Product Properties Test Guidelines
Cox, S. S., Hodgson, A. T. and Little, J. C. (2001), Measuring Concentrations of Volatile Organic
Compounds in Vinyl Flooring, Journal Air & Waste Management Association, Vol. 51, pp. 1195-1201
Guo, Z., Liu, X., Krebs, K. A., Roache, F. N. (2009). Perfluorocarboxylic Acid Content in 116 Articles of
Commerce, U.S. EPA, National Risk Management Research Laboratory, Research Triangle Park, NC,
Report No. EPA/600/R-09/033, 52 pp.
http://www.epa.gov/nrmrl/pybs/600r09033/600r09033.html
Health Canada (2014). Product Safety Laboratory Reference Manual. Method C-11.2. Determination of
Ethylene Glycol and Di-Ethylene Glycol in Consumer Products by GC/MS.
Health Canada (2015a). Product Safety Laboratory Reference Manual. Method C-ll.l. Determination of
alpha- pinene, D-limonene, and alpha-terpineol in Consumer Products by Gas Chromatography-
Mass Spectrometry (GC-MS) Using Solid Phase Extraction (SPE).
Health Canada (2015b). Product Safety Laboratory Reference Manual. Method C47. Sample
Preparataion Technique for the Determiniation of Flame Retardants in Textile, Foam, and Other
Similar Consumer Products.
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2. Emissions from Water and Aqueous Solutions to Indoor Air
2.1. Purpose:
The objective of this protocol is to collect information on chemical emissions from contaminated water
or commercial aqueous solutions into air through chamber testing. A key parameter to be determined is
the overall mass transfer coefficient.
2.2. Modifications:
This protocol is general, and it is anticipated that during protocol development and finalization,
additional modifications will be made to tailor the sampling parameters or analytical techniques to the
specific chemical and product tested, as well as to Agency recommendations specific to particular
products, chemicals, or exposure scenarios of interest. The overall mass transfer coefficients obtained
from this protocol are for chemical emissions from water pools. The results may not be applicable to
water jets and droplets, such as in the case of showering.
2.3. Description:
2.3.1. Approach
Contaminated tap water and water-based household products can be sources of a wide range of
hazardous chemicals, including elements (e.g., chlorine and radon), inorganic compounds (e.g.,
ammonia, hydrogen chloride, and chlorine dioxide), formaldehyde, chlorinated organic solvents (e.g.,
chloroform and trichloroethylene), and common VOCs (e.g., benzene, toluene, and xylene). Chemical
concentrations in indoor air are needed to assessinhalation exposure to the chemicals emitted from
water and aqueous solutions. Indoor air concentrations can be obtained from either measurements or
mathematical modeling. The key parameters that control the source strength are:
Content of the target chemical in the liquid phase;
Source area;
Water temperature;
Henry's law constant; and
Overall mass transfer coefficient.
The content of the target chemical in the liquid phase is usually obtained from source characterization
or product formulation. The Henry's law constant can be obtained from the literature (e.g., Sanders,
2015; NIST, 2016), quantitative structure-activity relationship (QSAR) models, or experimental
measurement. The exposed area and temperature of the source is relatively easy to determine or
estimate in most cases. Thus, determination of the overall mass transfer coefficient is essential in
predicting air concentrations. This protocol describes an experimental method for determination of the
overall and liquid-phase mass transfer coefficients that are associated with water use and applications
of water-based household products under simulated indoor conditions.
The experimental method described below is based on the studies by Guo & Roache (2003) and Liu, et
al. (2015). The general experimental procedure is as follows:
Prepare an aqueous solution with known concentration of the target chemical;
Set the small-scale environmental chamber at desired temperature, air change rate, and air
speed;
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Place a petri dish on the chamber floor;
Pour the aqueous solution into the petri dish, flush with the rim;
Close the chamber lid and start the test;
During the test, collect air samples periodically and record the air change rate, relative humidity,
air temperature and liquid temperature;
Conduct a separate chamber test with pure water under the same experimental conditions.
The results of liquid sample test are used to estimate the overall liquid-phase mass transfer coefficient
for the target chemical. The results of water evaporation test are used to estimate the gas-phase mass
transfer coefficient for water vapor, which is needed to estimate the liquid-phase mass transfer
coefficient for the target chemical.
A schematic of the experimental setup is shown in Figure 1. The procedure for testing agitated liquid is
similar except that the petri dish is placed on a magnetic stirrer (Figure 2).
The experimental results are analyzed by using a statistical routine that can handle mathematical
models in the form of ordinary differential equations and a routine that solves a nonlinear equation.
Many commonly used statistics software, such as MATLAB, SAS, SPSS, and data-fitting software, such as
SCIENTIST, have such capabilities.
Clean dryair
Incubator
DC fan
Small Chamber
Aqueous
solution
Petri dish
Thermocouple
f
Sampler
I
Pump
Figure 2. Experimental setup for determination of overall mass transfer coefficient for still water or aqueous
solution.
Page 12
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Incubator
DC fan
Clean dry air
Small Chamber
r
Sampler
Thermocouple
Magnetic stirrer -3^
Stir bar
Pump
Figure 3. Experimental setup for determination of overall mass transfer coefficient for agitated water or
aqueous solution.
2.3.2. Theoretical Considerations
2.3.2.1. The Emission Model
The rate of chemical emission from contaminated water or aqueous solution can be described by the
two-resistance theory with Equation 2-1 or, equivalently, 2-2 (Layman et al., 1990):
R = A Kol (CL - ฃ) (2-1)
R = A Kog (ClH - C) (2-2)
where R = emission rate (i-ig/h)
A = exposed area of liquid (m2)
Kol = overall liquid-phase mass transfer coefficient (m/h)
Kog = overall gas-phase mass transfer coefficient (m/h)
CL = chemical concentration in water (ng/m3)
C = chemical concentration in air (ng/m3)
H = dimensionless Henry's law constant and H = CG/ CL at equilibrium.
Note that, in some cases, parameters A and K0l are lumped together, forming a new parameter, AK0l,
known as the volumetric overall liquid-phase mass transfer coefficient.
The two mass transfer coefficients, K0l and K0g, are defined by Equations 2-3 and 2-4, respectively:
1 1,1
1 (2-3)
Kql fei H
Page 13
-------
where kL = liquid-phase mass transfer coefficient (m/h)
kG = gas-phase mass transfer coefficient (m/h).
Kol or Kog can be determined experimentally or estimated from kL, kG, and H. The method described
below allows for determinations K0l or K0g, from which kL and kG can also be estimated.
2,3,2,2, The Chamber Model for the Target Chemical
When a small liquid pool is placed in an environmental chamber, the chemical concentrations in air and
liquid are determined by Equations 2-5 and 2-6, respectively.
V^ = AKol(cl-^)-QC (2-5)
^ = -AK0L(cL-ฑ) (2-6)
where V= chamber volume (m3)
C = chemical concentration in chamber air (ng/m3)
t = elapsed time (h)
Q = air change flow rate (m3/h)
CL = chemical concentration in liquid, from Equation 2-7 (ng /m3)
WL = amount of target chemical remaining in the liquid (ng).
cL = (2"7)
VLO~ mv
where WL = amount of target chemical remaining in liquid (ng)
VLo = initial volume of liquid (m3)
Vw = volume of water evaporated at time t, from Equation 2-8, (m3).
Vw=If1 (2-8)
Pw
where rw = water evaporation rate, determined experimentally (g/h)
pw =density of water (g/m3).
Equations 2-5 and 2-6 can be solved numerically with a set of initial conditions, such as t = 0, C = 0, and
WL = VLo x CLo, where VLo is initial liquid volume (m3) and CLo is the pre-determined initial chemical
concentration in the liquid ng /m3). Because the air concentration is determined experimentally and
other parameters (V, Q, A, H, and CLo) are known, K0l is the only unknown parameter in Equations 2-5
and 2-6 and can be estimated by fitting the experimental data to the model.
Page 14
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2.3.2.3. The Chamber Model for Water Evaporation
The overall mass transfer coefficient (K0l or K0g) determined by this protocol is specific to the test
conditions. To make the results applicable to other conditions, it is desirable to break K0l or K0g into
three components as shown in Equations 2-3 and 2-4: the gas-phase mass transfer coefficient (kG), the
liquid-phase mass transfer coefficient (kL), and the dimensionless Henry's law constant (H). This can be
achieved by experimental determination of the gas-phase mass transfer coefficient for water (kGw), from
which the gas-phase mass transfer coefficient for the target chemical, kG, can be estimated.
When a small pool filled with pure water is placed in an environmental chamber, the moisture content
in air is determined by Equation 2-9.
dC,
V^ = Akcw (Cv - Cw)-Q (Cin - Cw)
0)
where Cw = water vapor concentration in air (g/m3)
ksw = gas-phase mass transfer coefficient for water evaporation (m/h)
Cv = saturated water vapor concentration at a given temperature (g/m3)
Cin = water vapor concentration in inlet air; C, = 0 for dry air (g/m3).
If dry air is used in the test (i.e., C, = 0) and if the initial condition is t = 0 and Cw = 0, the exact solution
to Equation 2-9 is:
r =
L kGW Cv
(l-
,-(L fecw+JV) t
)
(2-10)
The total amount of water evaporated during the test period (r) can be determined by integrating
Equation 2-10:
Wtot = Q
L k
GW Lv
L k-Qw+N
(2-11)
1- e~(LkGW+N)'
L kcw+N
+ 7
Lk
GW LV
LkGW+Q
[1
,-(L kGW+N) t
]
where Wtot = total amount of water evaporated during the test period (g)
N = air change rate and N = Q/V (h-1).
The complete derivation of Equation 2-11 is provided in Appendix 2-A.
Under the steady-state condition, it becomes:
w>ฐ< = fSs [ซ(T" ntm) + v] i2"12)
Page 15
-------
If Wtot is determined experimentally, the gas-phase mass transfer coefficient for water vapor, kGw, is the
only unknown in Equations 2-11 and 2-12.
233. Facility and Apparatus
Small-scale environmental chamber conforming to ASTM D-5116 (ASTM, 2010)
Top loading balance with a capacity of 500 g and an accuracy of 0.001 g
Laboratory magnetic stirrer with a plate size no less than 12 cm x 12 cm and a stir range of 100
to 1000 rpm
PTFE coated stir bars
Glass or polystyrene petri dish with an inside diameter of 6 to 9 cm and a depth of 2 to 3 cm,
serving as the container of the test solution
Small digital temperature sensor for monitoring liquid temperature
250-mL Erlenmeyer flasks with screw caps for transfer of test solution
Disposable glass pipettes for transfer of test solution
Reagent grade water for preparing test solutions
23.4. Experimental Methods
2,3,4,1, Determination of the Overall Moss Transfer Coefficient for Still Water or Aqueous
Prepare the test solution
Prepare a dilute aqueous solution of the target chemical. The concentration of the chemical and its
Henry's law constant at the set temperature should be accurately known. For testing a commercial
aqueous solution, dilution may be needed, especially for concentrated formulations.
Set chamber conditions
Set the chamber to the following conditions:
Place an empty clean petri dish at the center of the chamber floor.
Run the empty chamber for at least 2 hours.
Collect an air sample for the chamber background to ensure that the chamber is free of
contamination.
Prior to chamber test
Calibrate the top-loading balance and place it next to the incubator that houses the chamber.
Transfer the test solution into a 250-mL Erlenmeyer flask, enough to fill the petri dish.
Solution
o Air change rate
o Airspeed
o RH in inlet air
o Temperature
lh1
5 to 15 cm/s (controlled by the D.C. fan)
0 (dry air)
25 ฐC for base case or specified elevated temperature.
Page 16
-------
Place the capped flask in an incubator set at the test temperature for at least 2 hours
Open chamber lid.
Weight the empty petri dish and place it back to the chamber.
Remove the Erlenmeyer flask with solution from the incubator and weigh it.
Carefully pour the solution in the flask into the petri dish to nearly full.
Use a disposable pipette to transfer more solution to the petri dish until the liquid level is flush
with the rim of the dish.
Weigh the capped flask again.
Place the digital thermocouple temperature sensor into the solution. The probe should be
submerged and close to the surface of the liquid.
Close the chamber lid and record the test start time.
Air sampling during test
Take at least 10 air samples (excluding duplicate samples) over an 8-hour test period. A typical sampling
schedule is at 0.5, 1, 1.5, 2, 3, 4, 5, 6, 7, and 8 elapsed hours. At least 10% of samples should be taken in
duplicate, including the first and last samples.
After chamber test
Open the chamber lid and record the test end time.
Remove the petri dish with solution and weigh it.
2.3.4.2. Determination of the Overall Mass Transfer Coefficient for Agitated Water or Aqueous
Solution
The experimental setup and procedure for testing emissions from agitated water or aqueous solutions
are similar to those for testing still liquid except that a magnetic stirrer is used (see Figure 2 above).
According to Liu et al. (2015), the magnitude of the overall liquid-phase mass transfer coefficient (K0l) is
greater for agitated liquid than for still liquid. However, the difference in K0l between different levels of
agitation is rather small. Therefore, this protocol suggests the solution be tested at a single agitation
level. The criterion of selecting the sir bar size and speed setting is such that the magnetic stirrer
provides adequate agitation but without producing errant movement or spillage of the solution (Liu et
al., 2015).
2.3.4.3. Determination of the Gas-Phase Mass Transfer Coefficient for Water Evaporation
The procedure for water evaporation tests is similar to that for testing the target chemical except that
air sampling is not needed.
2.3.5. Test Matrix
2.3.5.1. Tests at a Single Temperature
For a given chemical and a given temperature, four tests are required (Table 2).
Page 17
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Table 2. Test Matrix for Emissions from Water or Aqueous Solutions to Indoor Air
Test ID
Target chemical
or pure water
Agitation
status
Test procedure
1
Target chemical
Still
2.3.4.1
2
Pure water
Still
2.3.4.3
3
Target chemical
Agitated
2.3.4.2
4
Pure water
Agitated
2.3.4.3
2.3,5.2. Tests at Different Temperatures
To determine the temperature dependence of the overall or phase mass transfer coefficients, tests
listed in Table 1 should be conducted at four temperatures. For chemicals with modest or small Henry's
law constant (H < 0.01), tests at 25, 35, 45, and 55 ฐC are recommended. For chemicals with a large
Henry's law constant (H > 0.01), tests at 25, 30, 40, and 45 ฐC are recommended.
2.3.6. Data Analysis
2.3,6.1. Estimation of the Overall Liquid-Phase Mass Transfer Coefficient for Target Chemical (K0l)
Data obtained from Section 2.3.4.1 are time-concentration pairs. The overall liquid-phase mass transfer
coefficient for the target chemical (/Cot) is estimated by fitting the data to Equations 2-5 through 2-8. The
water evaporation rate in Equation 2-8 is calculated from
w0- w1
(2-13)
where rw = water evaporation rate (g/h)
Wo = weight of the Erlenmeyer flask with test solution before filling the petri dish (g)
Wi = weight of the Erlenmeyer flask with test solution after filling the petri dish (g).
Note that, although each statistics software has its own syntax, the data fitting algorithm is similar.
Appendix 2-B provides a set of pseudo code, which can be tailored to different statistics software.
2.3.6.2. Estimation of the Gas-Phase Mass Transfer Coefficients for Water Vapor (kGW) and Target
Chemical (kG)
The gas-phase mass transfer coefficient for water vapor (kGw) is estimated by solving non-linear
Equation 2-11, where the total amount of water evaporated (Wtot) is calculated by using Equation 2-13.
For solving the nonlinear equation (Equation 11), it is recommended to use kGw = 10 m/h as the initial
estimate.
The gas-phase mass transfer coefficient for the target chemical (kG) can be calculated from Equation 2-
14 (Liu etal., 2015):
kGW
kG
2/3
(t) p-14>
where Dw and D are the gas-phase diffusion coefficients for water vapor and target chemical.
Page 18
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2.3.6.3. Estimation of the Liquid-Phase Mass Transfer Coefficient for the Target Chemical (kL)
Equation 2-3 can be rewritten as
KOL feG H
k, =
kG H - Kql
where K0l, kG, and H are all known.
(2-15)
2.3.6.4. Temperature dependence of the overall mass transfer coefficient
The overall mass transfer coefficient obtained at different temperatures can be analyzed by plotting K0l
versus the reciprocal of the absolute temperature, 1/T(K), on a semi-log scale. See Figure 4 as an
example. Linear regression for ln(K0i_) versus 1/T yields the following relationship:
In (Kol) = a + -
where constant a is the intercept of the regression line and b the slope.
(2-16)
1.00E-03
1.00E-04
o
1.00E-05
In K0,= 2.29-3730/T
0.003 0.00305 0.0031 0.00315 0.0032 0.00325 0.0033 0.00335 0.0034
1/T (K)
Figure 4. Overall liquid-phase mass transfer coefficient versus 1/T(K). Data points are hypothetical.
The method described above is also applicable to the liquid-phase mass transfer coefficient.
2.4. Records Retention and Reporting Results:
2.4.1. Records to be Maintained
Records submitted to the EPA should include, but are not limited to, the following:
a. The original signed protocol and any amendments.
b. Identification and characterization of the test substance as provided by Sponsor.
c. Identification and characterization of the material in question.
Page 19
-------
d. Experiment initiation and termination dates.
e. Laboratory log books (e.g., stock solution concentration calculations and solution preparation,
calibration, and QC data).
f. Instrument (e.g., small chamber system and analytical instrument) data files.
g. Spreadsheet files for data processing.
h. Environmental data acquired by the data acquisition system of the test chambers (e.g.,
temperature, air flow and inlet air moisture content).
i. Chain of custody documentation, including sample storage and handling information,
j. Copy of final report.
2.4.2. Final Report
A final report of the results of the study should be prepared and submitted to the EPA. The final report
should include, but is not limited to the following, when applicable:
a. Name and address of facility performing the study.
b. Dates on which the study was initiated and completed.
c. Objectives and procedures stated in the approved protocol, including any changes in the original
protocol.
d. Identification and characterization of the test substance as provided by Sponsor.
e. A summary and analysis of the data and a statement of the conclusions drawn from the analysis.
f. A description of the transformations and calculations performed on the data.
g. A description of the methods used and reference to any standard method employed.
h. A description of the instrumentation utilized.
i. A description of the preparation of the test solutions, the test conditions, the testing
concentrations, and the duration of the test.
j. A description of sampling and analytical methods, including level of detection, level of
quantification, and references,
k. A description of test specimens and test matrix.
I. A description of the test results including measured values for individual chemicals of interest
for each matrix.
m. A description of all circumstances that may affect the quality or integrity of the data.
n. The name of the study director, the names of other scientists or professionals, and the names of
all supervisory personnel involved in the study,
o. The signed and dated reports of each of the individual scientists or other professionals involved
in the study, if applicable,
p. The location where the raw data and final report are to be stored.
q. A statement prepared by the Quality Assurance Unit listing the types of inspections, the dates
that the study inspections were made, a description of quality assurance and quality control
process, and the findings reported to the Study Director and Management,
r. A copy of all raw data including but not limited to instrumentation output, lab notebooks, and
data sheets, etc.
Page 20
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2.43. Changes to the Final Report
If it is necessary to make corrections or additions to the final report after it has been accepted, such
changes should be made in the form of an amendment issued by the Study Director. The amendment
should clearly identify the part of the study that is being amended and the reasons for the alteration.
Amendments should be signed and dated by the Study Director and Laboratory Quality Assurance
Officer.
2.4.4. Changes to the Protocol
Planned changes to the protocol should be in the form of written amendments signed by the Study
Director and approved by the sponsor's representative and submitted to EPA using procedures in 40 CFR
790.50. Amendments should be considered as part of the protocol and should be attached to the final
protocol. Any other changes should be in the form of written deviations signed by the Study Director
and filed with the raw data. All changes to the protocol should be indicated in the final report. Changes
to the test standard require prior approval from EPA using procedures in 40 CFR 790.55 (U.S. Code,
1999).
2.5. References:
ASTM (2010). D5116-10 Standard Guide for Small-Scale Environmental Chamber Determinations of
Organic Emissions from Indoor Materials/Products. West Conshohocken, PA: ASTM International.
http://www.astm.org/Standards/D5116.htm.
Guo, Z. and Roache, N. F. (2003). Overall Mass Transfer Coefficient for Pollutant Emissions from Small
Water Pools under Simulated Indoor Environmental Conditions, The Annals of Occupational Hygiene, 47:
279-286.
Lyman, W. L., Reehl, W. F., Rosenblatt, D. H. (1990). Handbook of chemical property estimation methods:
environmental behavior of organic compounds. American Chemical Society, Washington, DC.
Liu, X., Guo, Z., Roache, N. F., Mocka, C. A., Allen, M. R., and Mason, M. A. (2015). Henry's Law Constant
and Overall Mass Transfer Coefficient for Formaldehyde Emission from Small Water Pools under
Simulated Indoor Environmental Conditions. Environmental Science & Technology, 49:1603-1610.
NIST (2016). NIST Standard Reference Database Number 69. http://webbook.nist.gov/chemistry/
Sander, R. (2015). Compilation of Henry's Law Constants for Water as Solvent (Version 4.0), Atmospheric
Chemistry and Physics, 15: 4399-4981.
Appendix 2-A. Derivation of Equation 2-11 for Water Evaporation
2-A.l Mass balance for the Amount of Water Evaporated
During the water evaporation test, the total mass of water evaporated from the pool can be calculated
from mass balance equation 2-A1:
Wtot = Wout + Wc{t) - Wc{0) (2-A1)
where Wtot = total amount of water evaporated during the test duration (g)
Page 21
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Wout = amount of water vapor leaving the chamber (g)
I/I/c(t) = amount of water remaining in the chamber at time t (g)
l/l/c(0) = amount of water in the chamber at time = 0 (g).
If dry air is used for the test (i.e., l/l/c(0) = 0), Equation 2-A1 becomes:
Wtot = Wout + Wc (2-A2)
where Wtot = total amount of water evaporated during the test duration (g)
Wout = amount of water vapor leaving the chamber (g)
Wc = amount of water remaining in the chamber at the end of test (g).
2-A.2 Calculating water vapor concentration in the chamber {Cw)
For the dynamic process of water evaporation from a pool, the mass balance can be expressed by
Equation 2-A3:
v *ฃ> = A kcw (cv - Cw)-Q {Cin - Cw) (2-A3)
where V= chamber volume (m3)
Cw = water vapor concentration in chamber air (g/m3)
t = time (h)
A = source area (m2)
kow = gas-phase mass transfer coefficient for water evaporation (m/h)
Cv = saturated water vapor concentration at the chamber temperature (g/m3)
Q = chamber air flow rate (m3/h).
Cin = water vapor concentration in inlet air (g/m3).
If dry air is used for the tests (Cin = 0), Equation 2-A3 becomes:
V^ = Akcw (Cy - Cw)-Q Cw (2-A4)
Given the initial conditions: t = 0 and Cw = 0, Equation 2-A4 can be solved to give:
= LkowC^ U _ (L kw+N) f| (2_A5)
W Lkcw+N 11 V '
where L = loading factor and L = A/V (nr1)
N = air change rate and N = Q/V (h-1).
2 -A.3 Calculating the amount of water vapor leaving the chamber (M/out)
From Equation 2-A5, the average concentration of water vapor over the test period (t) is given by
CZ = -C cw dt = (! _ e-(LkGW+N)t\ dt (2
w t 0 T J0 L kcw+N V ' V
Page 22
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which yields:
-p _ i L k.QW Cv
Lw ~ r LkGW+N
T
I- e~(LkGW+N)T
L kcw+N
(2-A7)
Thus, the amount of water vapor leaving the chamber by the end of test can be calculated from
Wout = Q Cw t = Q
L kGW Cv
L fegj4/+iV
T
1 e-(L kGW+N)T
(2-A8)
2-A.4 Calculation of the amount of water remaining in the chamber {Wc)
The amount of water vapor remaining in the chamber at time t can be calculated from
Wc( t) = VCw(z)
where Cw(t) = water vapor concentration at the end of test (i.e., t = t).
Substituting Equation 2-A5 into 2-A9 yields:
Wc(t) = V
L kr,w+N
kcw+N) TJ
2-A.5 Calculating the total amount of water evaporated during the test (Wtot)
Substituting Equations 2-A8 and 2-A10 into 2-A2 gives
wtot = Q
L kcw cv
L kcw+N
T
1 e
~(L kcw+N)T
L kcw+N
+ V
L kcw Cy
L kcw+N
[1-
,-(L kcw+N) t]
(2-A9)
(2-A10)
(2-A11)
which can be simplified to:
wtot =
L kcw C1
L kCw+N
ฑ{Qt + (v ) [1-
N \ L kcw+N J L
,-(L kcw+N) T
]}
(2-A12)
Under the steady state condition, which is usually reached in less than one hour for water evaporation
in the test chamber, the exponential term in the equation approaches zero. Thus, Equation 2-A12 can be
further simplified to:
W;
tot
L kcw cv
L kcw+N
[
-------
Appendix B. Pseudo Code for Estimating the Overall Liquid-Phase Mass Transfer Coefficient
from Experimental Data
As described in Section 2.3.5.1, the overall liquid-phase mass transfer coefficient is estimated by fitting
the time-concentration data to Equations 2-5 through 2-8 by means of nonlinear regression. In this
Appendix, a set of pseudo code is provided, which can be tailored to different statistics software. Note
that the text after the double slash (//) are comments; they are not part of the code.
Dependent variables
C
WL
// chemical concentration in chamber air (ng/m3)
// amount of target chemical remaining in liquid (ng)
Independent variable
// elapsed time (h)
Unknown parameter
KOL // overall liquid-phase mass transfer coefficient (m/h)
Known parameters
V
Q
A
VLO
CLO
H
rw
rou
// chamber volume (m3)
// air change flow rate (m3/h)
// source area (m2)
// initial volume of liquid (m3)
// initial concentration in liquid phase (ng/m3)
// dimensionless Henry's law constant
// water evaporation rate (g/h)
// density of liquid water; rou = 1E6 (g/m3)
Model equations
ER = A * KOL* (CL-C/H)
C' = (ER-Q* C)/V
WL' = - ER
CL = WL / (VLO - rw * t / rou)
// ER = chemical emission rate (|ag/h)
// C' = dC/dt
// WL= chemical mass in liquid; WL' = dWL/dt
// chemical concentration in liquid phase (ng/m3)
Initial conditions
t = 0
C = 0
WL = VLO * CLO
Initial estimate for value of KOL
KOL = 0.001
Page 24
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3. Short-Term Emission Testing
3.1. Purpose:
The objective of this protocol is to collect information on chemical emission rates from products or
articles through chamber testing.
3.2. Modifications:
This protocol is general, and it is anticipated that during protocol development and finalization,
additional modifications will be made to tailor the sampling parameters or analytical techniques to the
specific chemical and product tested, as well as to Agency recommendations specific to particular
products, chemicals, or exposure scenarios of interest.
3.3. Description:
3.3.1. Approach
Chemical emissions from products and articles are most commonly tested in environmental chambers,
which are designed based on continuous stirred tank reactors (CSTR). Thus, many principals of the CSTR
are applicable to test chambers, including mixing, residence time, steady state, and the assumption that
the chemical concentration in the outlet air is representative of the chemical concentration inside the
chamber. A conventional chamber system consists of the chamber itself, clean air supply, air flow
control, air sampling ports, temperature and humidity sensors and controls, and a data acquisition
system. An electric fan is often installed in conventional small and large chambers to improve air mixing
and maintain certain air speed. Typical test conditions are 23ฐC, 50% relative humidity and 0.1 m/s air
speed. The air change rate varies depending on chamber type. Over time, progress has been made to
standardize testing for certain kinds of materials in certain kinds of chambers. The major chamber types
are summarized in Table . Additional standard methods based on the standards listed in Table 3 include
California Department of Public Health/Environmental Health Laboratory Branch (CDPH/EHLB) standard
method for California Specification 01350 (CDPH/EHLB, 2010), ASTM D6007, ANSI/BIFMA M7.1 and
ANSI/BIFMA x7.1.
Table 3. Commonly Used Environmental Chambers for Testing of Chemical Emissions from Products and Articles3
Chamber
Type
Typical
Size
Typical Air
Change Rate (h"1)
Commercially
Available
References
Full-scale
chamber
30 m3
1
No
ISO 16000-9
ASTM D6670
Small-scale
chamber
50 L
1
Yes
ISO 16000-9
ASTM D5116
Micro
chamber
0.05-0.25 L
>100
Yes
ISO 16000-25
ASTM D7706
Field and Laboratory
Emission Cells
0.035 L
>100
Yes
ISO 16000-10
ASTM D7143
aMid-scale chambers, typically 1 to 10 m3 in size, are also available but less commonly used.
Page 25
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3.3.2. Selection of Test Chambers
Selecting a chamber suitable for testing a given chemical in a given product or article depends on several
factors, including the properties of the chemical of interest and those of the substrate. A general
guideline is provided below.
3.3.2.1. Full Scale Chamber
The full-scale chamber is most suitable for testing volatile organic compound (VOC) emissions from
article assemblies, such as furniture, computers, TV sets, portable air cleaning devices, home electronics,
and office equipment. The full-scale chamber is costlier to operate than other types of chambers and
can accommodate testing of large items.
The full-scale chamber would also be appropriate for estimating VOC emissions from spray-applied
products. Additional sampling equipment may be desired to size aerosols. These include an aerodynamic
particle sizer (APS) or scanning mobility particle sizer (SMPS).
Activated alumina
Equipment impregnated with
low eniciency Mir
s air fIter conditioner
low eniciency Activatea poiassium High efficiency
air filter carbon filter permanganate air filter
room
Blower
Outdoor Low efficiency Air
air air filter conditioner
To outdoor
blower
Exhaust fan
Test room
Flowmeter
VOC i
sampling tube
Humiditer
Air sampler
VOC
Chamber
Figure 5. Schematic of example 30 m3 full-scale chamber (Liu et al., 2012).
3.3.2.2. Small Scale Chamber
The small-scale chamber is suitable for VOC emissions from a large variety of products and articles as
long as they can be cut into coupons or panels that fit the chamber size. It has limited capability for
testing SVOC emissions.
Page 26
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Temperalure C ontrolled Cabinet
Gas Sample
Gas Sample
Analysis
GC
Clean Air
Humidity
control
system
Diffuse*
Figure 6. Schematic diagram of small-scale VOC emission chamber (Yerramilli et al., 2010).
3,3.2.3. Field and Laboratory Emission Cell
The Field and Laboratory Emission Cell (FLEC) has a cone-shaped cavity and can be placed directly on the
surface of the test material, which becomes the bottom of the cell. Because of its small volume (35 mL)
and large source area (20 cm in diameter), FLEC has the largest loading factor among all test chambers.
It is mostly used to test VOC emissions from building materials with a flat and non-porous surface. It has
limited capability for testing SVOC emissions.
Silicon rubber foam
Screw
Air Outlet
Thermoelement
Volume
35ml
Air inlcl
Air inlet
FLEC
150mm
////zmm'/.i mmww
Figure 7. Schematic plot of Field and Laboratory Emission Cell (FLEC) (Kim et al., 2007)
Channel
Air outlet
Air inlet
b) <\
Sealing material
Slit
Page 27
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3,3.2.4. Micro Chamber
Micro chambers are small cells operated at a high
air exchange rate. These chambers are suitable for
rapid screening of material emissions and have
been used for both VOCs and SVOCs.
Micro chambers have a wider range of
temperature control than other types of chambers
and, thus, are more convenient for testing
emissions at elevated temperatures.
Testing of SVOC emissions is more challenging than
testing VOCs because the interior surfaces of the
test chamber can adsorb a significant amount of
SVOCs from air. In conventional test chambers and
FLEC, most SVOCs emitted from the source are
adsorbed by interior surfaces (Clausen et al., 2004).
This problem can be somewhat alleviated by using
micro chambers, which have a high air change rate and relatively small surface area. An alternative is to
use a specially-designed chamber that is modified to minimize the sink effect (Xu et al., 2012).
When the SVOC emissions cannot be detected at room temperature, testing at elevated temperatures
can be considered. In order to extrapolate the test results to normal temperature, tests should be
conducted at a minimum of three temperatures (see Appendix 3A).
3.3.3. Sample Preparation, Transport, Storage, and Conditioning
Most standards, including those shown in Table contain a section for sample preparation,
transportation, storage, and conditioning. The California standard method (CDPH/EHLB, 2010) contains
more details about this subject. There are also stand-alone standards for sample handling (e.g., ISO
16000-11). Appropriate procedures should be used to prevent samples from being contaminated by
exposure to contaminated air or materials and to prevent chemical loss due to exposure to light,
excessive moisture, and/or elevated temperature.
To prepare test specimens, flat products/articles are cut into coupons (or panels). The size of the test
specimen is often expressed as a loading factor (the exposed surface area divided by the volume of the
test chamber, in (m2/m3)). For the same test specimen, a large loading factor means higher
concentrations in chamber air, though this relationship may not be linear.
3.3.4. Generic Test Procedure
a. Prior to a test, clean the chamber according to the standard cleaning procedure for the selected
chamber.
b. Check the chamber for air leakage.
c. Flush the chamber with clean air at the specified air flow rate, temperature, and humidity; take
a background air sample to ensure that the chamber is free of contamination.
d. Open the lid (or door) of the chamber to place the test specimen(s) into the chamber (Note that
in conventional chambers, the test specimen is often placed in the center of the chamber fioor.
If chambers are of sufficient size, test specimens can also be placed vertically by using a rack to
increase the loading factor.
Sampling port
4 j^
Chamber
Figure 8. Photo of micro-chamber/
thermal extractor (jiCTE) from Schripp et al (2007)
Page 28
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e. Close and tighten the chamber lid (or door) and record the test start time.
f. Collect air samples according the sampling plan (see Sampling Methods section for more
details).
The test duration depends on the source type and data needs. To determine emission trends (constant
versus decaying emissions), a minimum of one week is recommended, during which at least six samples
should be taken at different elapsed time.
To calculate emission rates or emission factors for non-constant sources, more samples (e.g., a dozen)
are often needed. A greater sampling frequency is needed in the early hours of testing to capture rapidly
changing chamber concentrations. This is especially important for conventional test chambers.
33.5. Sampling Methods
Selection of the sampling method requires consideration of several factors, including collection
efficiency, specificity, capacity (potential breakthrough), and compatibility with the analytical methods.
Many general-purpose sampling methods have been developed for collecting VOCs and SVOCs from
chamber air, including sorbent tubes (Tenax, XAD resins, charcoal, silica gel etc.), impingers, filters, and
polyurethane foam (PUF) cartridges. There are also chemical specific sampling media. For example, 2,4
dinitrophenylhydrazine (DNPH) cartridges are commonly used for sampling aldehydes (ASTM D6803).
3.3.6. Sampling Volume
Successful collection of chemicals of interest in emission samples depends on the sensitivity of the
analytical methods and sample volume. A low sample volume may result in no detection of the chemical
of interest. Thus, it is important to roughly determine the proper sampling volume before commencing
testing. This is often achieved in two ways: (1) trial and error, which is done by conducting a pilot or
scouting test; and (2) estimating the order-of-magnitude of the air concentration based on existing mass
transfer models, from which a proper sample volume can be determined when the method
quantification limit is known. The latter method requires knowledge of mass transfer source models and
parameter estimation methods.
3.3.7. Sample Extraction and Analysis
Sample extraction protocols will vary based on the target compound of interest and air sampler used. In
general, Soxhlet extraction, sonication, solvent exchange, and sample concentration using nitrogen may
be required. Many standard methods can be used to analyze the air samples collected from chamber
testing (e.g., EPA Methods TO-Ol, TO-17, 8260B and 8270D; ASTM D 7339 and D 5197; ISO 16000-3 and
ISO 16000-6). Selection of appropriate analytical methods depends on the properties of the chemicals of
interest and the type of sampling media. Gas chromatography (GC) with different detectors (e.g., flame
ionization, electron capture, and mass spectrometry detectors) are most commonly used for VOC and
SVOC analysis. High performance liquid chromatography (HPLC) is often used for aldehydes and some
SVOCs. Commonly used detectors include UV, fluorescence, and tandem mass spectrometry.
3.4. Records Retention and Reporting Results:
3.4.1. Records to be Maintained
Records submitted to the EPA should include, but are not limited to, the following:
a. The original signed protocol and any amendments.
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b. Identification and characterization of the test substance as provided by Sponsor.
c. Identification and characterization of the material in question
d. Experiment initiation and termination dates.
e. Laboratory log books (e.g., stock solution concentration calculations and solution preparation,
calibration, and QC data).
f. Instrument (e.g., GC/ECNI) data files.
g. Spreadsheet files for data processing.
h. Environmental data acquired by the data acquisition system of the test chambers (e.g.,
temperature, air flow and inlet air moisture content).
i. Chain of custody documentation, including sample storage and handling information.
j. Copy of final report.
3.4.2. Final Report
A final report of the results of the study should be prepared and submitted to the EPA. The final report
should include, but is not limited to the following, when applicable:
a. Name and address of facility performing the study.
b. Dates on which the study was initiated and completed.
c. Objectives and procedures stated in the approved protocol, including any changes in the original
protocol.
d. Identification and characterization of the test substance as provided by Sponsor.
e. A summary and analysis of the data and a statement of the conclusions drawn from the analysis.
f. A description of the transformations and calculations performed on the data.
g. A description of the methods used and reference to any standard method employed.
h. A description of the instrumentation utilized.
i. A description of the preparation of the test solutions, the test conditions, the testing
concentrations, and the duration of the test.
j. A description of sampling and analytical methods, including level of detection, level of
quantification, and references.
k. A description of test specimens and test matrix.
I. A description of the test results including measured values for individual chemicals of interest
for each matrix.
m. A description of all circumstances that may affect the quality or integrity of the data.
n. The name of the study director, the names of other scientists or professionals, and the names of
all supervisory personnel involved in the study.
o. The signed and dated reports of each of the individual scientists or other professionals involved
in the study, if applicable.
p. The location where the raw data and final report are to be stored.
q. A statement prepared by the Quality Assurance Unit listing the types of inspections, the dates
that the study inspections were made, a description of quality assurance and quality control
process, and the findings reported to the Study Director and Management.
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r. A copy of all raw data including but not limited to instrumentation output, lab notebooks, and
data sheets, etc.
3.4.3. Changes to the Final Report
If it is necessary to make corrections or additions to the final report after it has been accepted, such
changes should be made in the form of an amendment issued by the Study Director. The amendment
should clearly identify the part of the study that is being amended and the reasons for the alteration.
Amendments should be signed and dated by the Study Director and Laboratory Quality Assurance
Officer.
3.4.4. Changes to the Protocol
Planned changes to the protocol should be in the form of written amendments signed by the Study
Director and approved by the sponsor's representative and submitted to EPA using procedures in 40 CFR
790.50. Amendments should be considered as part of the protocol and should be attached to the final
protocol. Any other changes should be in the form of written deviations signed by the Study Director
and filed with the raw data. All changes to the protocol should be indicated in the final report. Changes
to the test standard require prior approval from EPA using procedures in 40 CFR 790.55 (U.S. Code,
1999).
3.5. References:
ANSI/BIFMA M7.1-2011: Standard Test Method for determining VOC Emissions from Office Furniture
Systems, Components and Seating, available at:
https://www.bifma.org/store/ViewProduct.aspx?id=1375383
ANSI/BIFMA X7.1-2011 Standard for Formaldehyde and TVOC Emissions of Low-emitting Office Furniture
and Seating, available at https://www.bifma.org/store/ViewProduct.aspx?id=1375803
ASTM (2009). D5197 - 09el Standard Test Method for Determination of Formaldehyde and Other
Carbonyl Compounds in Air (Active Sampler Methodology)
ASTM (2010). D5116-10 Standard Guide for Small-Scale Environmental Chamber Determinations of
Organic Emissions from Indoor Materials/Products, available at
http://compass.astm.org/EDIT/html annot.cgi?D5116+10
ASTM (2011a). D7143 -11 Standard Practice for Emission Cells for the Determination of Volatile Organic
Emissions from Indoor Materials/Products, available at http://www.astm.org/Standards/D7143.htm
ASTM (2011b). D7706-11 Standard Practice for Rapid Screening of VOC Emissions from Products Using
Micro-Scale Chambers, available at http://www.astm.org/Standards/D7706.htm
ASTM (1012). D7339 - 12 Standard Test Method for Determination of Volatile Organic Compounds
Emitted from Carpet using a Specific Sorbent Tube and Thermal Desorption / Gas Chromatography.
https://www.astm.org/Standards/D7339.htm
ASTM (2013). 6670-13 Standard Practice for Full-Scale Chamber Determination of Volatile Organic
Emissions from Indoor Materials/Products, available at http://www.astm.org/Standards/D6670.htm
ASTM (2013). ASTM D6803-13 Standard Practice for Testing and Sampling of Volatile Organic
Compounds (Including Carbonyl Compounds) Emitted from Paint Using Small Environmental
Chambers, available at http://www.astm.org/Standards/D6803.htm
ASTM (2014). D6007-14 Standard Test Method for Determining Formaldehyde Concentrations in Air
from Wood Products Using a Small-Scale Chamber, available at
http://www.astm.org/Standards/D6007.htm
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CDPH/EHLB (2010). Standard Method VI.1, Standard method for the testing and evaluation of volatile
organic chemical emissions from indoor sources using environmental chambers, Version 1.1,
available at
https://www.scsglobalservices.com/files/standards/CDPH EHLB StandardMethod VI 1 2010.pdf
Clausen, P., Hansen, V., Gunnarsen, L., Afshari, A., Wolkoff, P. (2004). Emission of di-2-ethylhexyl
phthalate from PVC Flooring into Air and Uptake in Dust: Emission and Sorption Experiments in FLEC
and CLIMPAQ. Environmental Science & Technologies, 38, 2531-2537.
Cleanroom Technology (2011). VOC emissions test method, available at
http://www.cleanroomtechnology.com/
technical/article page/VOC emissions testULmethod/58849
EPA (2011). Quality Management Tools - QA Project Plans. http://www.epa.gOv/Q.UALlTY/qapps.html
ISO (2006a). ISO 16000-9: Indoor Air-Part 9: Determination of the Emission of Volatile Organic
Compounds from Building Products and Furnishing-Emission Test Chamber Method, available at
http://www.iso.org/iso/catalogue detail.htm?csnumber=38203
ISO (2006b). ISO 16000-10:2006 -- Indoor air -- Part 10: Determination of the Emission of Volatile
Organic Compounds from Building Products and Furnishing -- Emission test cell method, available at
http://www.iso.org/iso/iso catalogue/catalogue tc/catalogue detail.htm?csnumber=38204
ISO (2006c). ISO 16000-11:2006 Indoor air -- Part 11: Determination of the Emission of Volatile Organic
Compounds from Building Products and Furnishing -- Sampling, storage of samples and Preparation
of Test Specimens. http://www.iso.org/iso/catalogue_detail.htm?csnumber=38205
ISO (2011a). ISO 16000-3:2011 Indoor air -- Part 3: Determination of Formaldehyde and other Carbonyl
Compounds in Indoor Air and Test Chamber Air -- Active sampling method.
http://www.iso.org/iso/catalogue detail.htm?csnumber=51812
ISO (2011b). ISO 16000-6:2011 Indoor air - Part 6: Determination of Volatile Organic Compounds in
Indoor and Test Chamber Air by Active Sampling on Tenax TA sorbent, thermal desorption and gas
chromatography using MS or MS-FID.
http://www.iso.org/iso/catalogue_detail.htm?csnumber=52213
ISO (2011c). 16000-25, Indoor Air-Part 25: Determination of the Emission of Semi-Volatile Organic
Compounds by Building Products -Micro-chamber method.
http://www.iso.org/iso/catalogue_detail. htm?csnumber=44892
Kim S, Kim J, and Kim H (2007). Application of Field and Laboratory Emission Cell (FLEC) to Determine
Formaldehyde and VOCs Emissions from Wood-Based Composites. Mokchae Konghak 35(5): 24-37.
Liu W, Zhang Y, and Yao Y (2012). Labeling of Volatile Organic Compounds Emissions from Chinese
Furniture: Consideration and practice. Chinese Science Bulletin, 58: 3499-3506
Liu, X, Guo, Z., Krebs, K.A., Stinson, R.A., Nardin, J.A., Pope, R.H., Roache, N.F., (2015) Chamber study of
PCB Emissions from Caulking Materials and Light Ballasts, Chemosphere, 137, 115-121. (Figure in SI)
Schripp, T., et al. (2007) "A Microscale Device for Measuring Emissions from Materials for Indoor Use."
Analytical and bioanalytical chemistry 387.5: 1907-1919.
U.S. Code (1999). 40 CFR 790.55 - Modification of Test Standards or Schedules During Conduct of Test.
https://www.gpo.gov/fdsvs/granule/cfr-1999-title40-vol24/cfr-1999-title40-vol24-sec790-
55/content-detail.html
US EPA (1984). Method TO-Ol Method for the Determination of Volatile Organic Compounds in
Ambient Air using Tenaxฎ Adsorption and Gas Chromatography/Mass Spectrometry (GC/MS).
https://www3.epa.gov/ttnamtil/files/ambient/airtox/to-l.pdf
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US EPA (1996). Method 8260B Volatile Organic Compounds by Gas Chromatography/Mass Spectrometry
(GC/MS). https://www.epa.gov/sites/prodyction/files/Z015-lZ/documerits/8260b.pdf
US EPA (1999). Compendium Method TO-lOA -- Determination Of Pesticides And Polychlorinated
Biphenyls In Ambient Air Using Low Volume Polyurethane Foam (PUF) Sampling Followed By Gas
Chromatographic/Multi-Detector Detection (GC/MD).
https://www3.epa.gov/ttnamtil/files/ambient/airtox/to-10ar.pdf
US EPA (2014) Method 8270D: Semi volatile Organic Compounds by Gas Chromatographv/Mass
Spectrometry (GC/MS). available at
http://www3.epa.gov/epawaste/hazard/testmethods/sw846/pdfs/8270d.pdf
Xu Y, Liu Z, Park J, Clausen PA, Benning JL, and Little JC (2012). Measuring and Predicting the Emission
Rate of Phthalate Plasticizer from Vinyl Flooring in a Specially-Designed Chamber. Environmental
Science and Technology, 46: 12534-12541.
Yerramilli S, Schiller R, Downie R, and Garnys V (2010). Measurement of Chemical Emissions from
Building Products. The Australian Building Services Journal, 1: 41-44.
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Appendix 3-A. Micro Chamber Method
3-A.l General Method Description
This protocol uses a modified micro chamber method to characterize emissions of chemicals of interest
from articles or products at modestly elevated temperatures. The test results will be used to estimate
the emission rates at a given temperature, including room temperature. Micro chambers are made of
stainless steel, often with the interior surfaces coated with an inert material. The size of the micro
chamber may vary, typically from 44 to 250 mL. Chemicals emitted from the test specimen are carried
out of the chamber by well characterized air flow and captured by a sampler at the chamber's outlet
port. The general steps for testing the chemical of interest emissions from articles are as follows:
a) Prepare test specimens by cutting the article into circular disks, where size is determined by
the inside diameter of the micro chamber body;
b) Prepare the micro chamber system, including air flow calibration, relative humidity,
temperature, and pressure settings;
c) Conduct chamber testing while collecting air samples directly from the chamber outlet at
different elapsed times; the results are used to calculate WA in Equation 3-A3;
d) After the last air sample is taken, take rinse/wipe samples from the interior surfaces of the
chamber to determine Wc in Equation 3-A2;
e) Calculate the time-averaged area-specific emission rate using Equation 3-A2.
3A.2 Micro Chamber System
A micro chamber system consists of the following components:
a)
b)
c)
d)
e)
f)
Several identical micro chambers.
A clean air supply, usually clean air generator or zero air stored in a compressed cylinder
with a gas tank regulator that is capable of sustaining 60 psi of pressure.
An air humidifier (optional).
An air flow distribution system that maintains a constant flow of air through each chamber,
independent of sorbent tube impedance and whether or not a sorbent tube is attached.
A temperature control system, which allows tests to be conducted at room or modestly
elevated temperatures.
An air sampling port, which allows the air sampler to be inserted directly into the air outlet
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Figure 9. An example of a micro chamber system. Note that the
Polyurethane Foam (PUF) air samplers are directly connected to the
chamber air outlet (Liu et al 2015).
For the purpose of calculating the area-specific emission rate, the exact area of the exposed surface of
the test specimen should be known. This can be done by placing a special type of sample holder, such as
a sample spacer with a circle plate on top, inside the chamber to raise the test specimens to the top of
the chamber so only the emissions from the top surface of the test specimen are collected by the air
sampler. Operating the micro chamber in this manner is known as the "cell mode" (ASTM, 2011b).
3-A.3 Calculations
Under the steady-state condition, the area-specific emission rate for VOCs is calculated from Equation
3A-1.
E = (3A-1)
where E = area-specific emission rate (ng/m2/h),
Q = air change flow rate (m3/h),
C = chemical concentration in chamber air (ng/m3),
A = exposed area of the test specimen (m2).
However, Equation 3A-1 is not applicable to testing SVOCs because the interior surfaces of the chamber
may adsorb significant amount of chemicals, which should be considered when calculating the emission
rate. To resolve this problem, the existing test method requires a second step to characterize the
adsorption after emission testing is complete (ISO, 2011), which complicates emissions testing. The
current protocol simplifies the existing protocol by collecting rinse and wipe samples from chamber
walls at the end of the emission test, as described in Section 3A.4.3.4 of this Appendix. With the
experimental data for air concentrations and adsorption by chamber walls, the time-averaged area-
specific emission rate can be calculated from Equation 2:
E = (3A-2)
AXt
where E = time-averaged area-specific emission rate over the test duration (ng/m2/h),
WA = amount of chemical of interest leaving the micro chamber, from Equation 3 (ng),
Wc = amount of chemical of interest adsorbed by chamber walls, which is experimentally
determined (see Section A.4.3.4 of this Appendix) (ng),
A = source area (m2),
t = test duration (h).
According to ASTM D5116, (ASTM, 2010), WA can be calculated from Equation 3A-3, which is applicable
to both VOCs and SVOCs:
jat rt rn-1 (Q+1+ Q) x (fj+l ^i)
"'A V Li = 0 2
(3A-3)
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where Q = air change flow rate (m3/h),
C Ch-i = chemical concentrations in chamber air in the ith and (i+l)th air samples (ng/m3),
t,-, tj+i = sampling times for the ith and (i+l)th air samples (h),
n+1 = number of air samples collected, including the one for chamber background (i.e., C0 at
t=0).
If the tests are conducted at several temperatures, a semi-log plot of the area-specific emission rate
against the reciprocal of the temperature is expected to show a linear relationship (Figure 10), which
can be used to estimate the emission rate at a given temperature, including room temperature, typically
23 degrees Celsius.
100
(N
10 --
0.00315 0.0032 0.00325 0.0033 0.00335 0.0034 0.00345
l/T (K)
Figure 10. An example of area-specific emission rate (E) as a function of
temperature based on data from micro chamber tests.
The tests should first be conducted at the highest temperature (i.e., Tests 1-A and 1-B in Table 4),
followed by the second highest temperature and so on. No further tests are needed whenever both of
the following conditions are met:
1. Two thirds of the air samples in duplicate tests are below the method detection limit,
2. The rinse/wipe samples collected from the interior surfaces of the chambers in duplicate tests
are both below the method detection limit.
An example of the test matrix is given in Table 4. Note that the temperatures given in Table 4 are for
demonstration purpose only. Temperature selection should be done on a case-by-case basis. Conducting
trial testing usually helps.
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Table 4. An Example of Test Matrix and
Temperature Settings for Micro Chamber Tests.
Other conditions, such as chamber air flow rate,
relative humidity, sample volume, number of
samples, and sample duration, will be determined
for target compounds.
3A.4 General Test Procedure:
3A.4.1 Preparation of the Micro Chamber System
a. The micro chambers should be cleaned
prior to each test by washing all of the
interior surfaces with de-ionized water and
detergent, then rinsing the interior surfaces
with solvent such as acetone followed by
hexane.
b. The micro chamber unit can be operated in
a ventilated fume hood.
c. Make certain the gas cylinder is turned off
and the power switch of the micro chamber
unit is off.
d. Connect the air supply line to the air inlet of
the micro chamber unit.
e. Switch power of the micro chamber unit to on position.
f. Turn on the air supply gas at the tank.
g. Set the oven temperature to the desired temperature (e.g., 35 ฐC in Table 4).
h. Set the gas tank regulator to desired pressure and then use the air flow calibrator to measure
the air flow at the inlet and then outlet points for each micro chamber to be used. The outlet
gas flow rate should be no less than 90% of the inlet gas flow rate measured at the same
temperature and humidity conditions.
i. To calibrate the air flow at other temperatures (e.g., 45, 55 and 65 ฐC in Table 4), repeat the
above two steps.
j. Create a chart by plotting the air flow again the gas pressure (Figure 11). The gas tank pressure
can be used in subsequent tests to set chamber air flow. This can be done by plotting air flow vs
gas pressure for the desired flow range.
k. Connect an air sampler to the chamber outlet port. The sampler should be suitable to collect air
samples for the given target compounds and at the test temperature.
I. Check the air flows at the inlet and outlet points for each chamber.
Test ID
Temperature (ฐC)
1-A
65
1-B
65
2-A
55
2-B
55
3-A
45
3-B
45
4-A
35
4-B
35
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0
0 10 20 30 40 50 60
Pressure (psi)
Figure 11. An example of the relationship between the inlet air flow rate and air
pressure at the gas tank regulator. Note that the calibration curves at different
temperatures may be slightly different.
3A.4.2 Air Sampling Method
Air samples are collected by connecting an appropriate air sampler (such as PUF) directly to the chamber
outlet (Figure 9). Thus, the sampling air flow is equal to the outlet air flow. This data allows for
calculation of the amount of chemical leaving the chamber (Equation 3A-3).
3A.4.3 Conducting Chamber Tests
3A.4.3.1 Set test conditions:
a. Place a pre-cleaned sample spacer into the chamber if needed.
b. Close the chamber lid.
c. Set the pressure to reach the desired air flow rate and temperature as determined during
preparation of the micro chamber system.
d. Check the air flow at the chamber outlet.
e. Flush the chambers with clean air for an appropriate time period based on the objective of the
test.
3A.4.3.2 Collect Background Air Sample
Background air samples are collected by placing the same type of sampler as used for the test on the
outlet port of the empty chamber. Background air samples are to collected for the same sampling
duration and sample volume as for a test sample.
3A.4.3.3 Test Chemical of Interest Emissions from Test Specimens
a) Open chamber lid and place a test specimen on the bottom of the chamber or sample
spacer.
b) Close chamber lid.
c) Record test start time (Note, The test start time is the time the chamber is sealed, but the
sampling start time can be any time after that, for example, immediately after the chamber
is sealed, after 1 hour or 24 hours or longer).
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d) Leave the chamber operating for an appropriate time period based on the objective of the
test.
e) Connect an appropriate air sampler to the outlet port of the chamber.
f) Record the sampling start time.
g) Collect air sample.
h) Disconnect the air sampler.
i) Record the sampling end time, the sampling time is the mid-point of the sampling duration.
j) Seal the sampler with proper fittings, if supplied, wrap the PUF sampler with two layers of
aluminum foil and store the sample in a refrigerator at 4 ฐC until extraction.
k) Collect additional air samples according the sampling schedule. Samples should be collected
at intervals throughout the sampling duration to effectively characterize changes in
emissions over time based on chemical and product of interest.
I) Record test end time.
3A.43.4 Collecting Rinse/Wipe Samples from Chamber's Interior Surfaces
a) Remove the micro chamber from the system.
b) Use a disposable glass pipette to transfer approximately 3 mL hexane (or appropriate
solvent, depending on the target chemical) into the chamber.
c) Use the pipette to draw the hexane solvent from the chamber to rinse the interior walls and
the sample spacer.
d) Use the pipette to transfer the rinse solvent to a 50-mL scintillation vial.
e) Repeat steps for rinsing the walls and transferring the rinse solvent two more times.
f) Use disposable forceps to fold and then hold a half-sized gauze wipe pad.
g) Wet the gauze wipe pad with 3-mL appropriate solvent.
h) Wipe the chamber lid thoroughly.
i) Place the wipe into the vial for storing the rinse liquid.
j) Repeat steps for wiping with the solvent-soaked (3-mL) gauze one more time.
k) Add 20 mL solvent to the vial.
I) Add 50 ng recovery standard to the vial and close the cap tightly.
m) If the sample is not extracted immediately, store it in a refrigerator at 4 ฐC. Appropriate
length of storage time and temperature will vary and should be documented.
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4. Long-Term Emission Testing - Partition and Diffusion Coefficients
4.1. Purpose:
The objective of this protocol is to collect information on physical/chemical properties that influence
migration rates of VOCs and SVOCs into the indoor environment.
4.2. Modifications:
This protocol is general, and it is anticipated that during protocol development and finalization,
additional modifications will be made to tailor the sampling parameters or analytical techniques to the
specific chemical and product tested, as well as to Agency recommendations specific to particular
products, chemicals, or exposure scenarios of interest.
4.3. Description:
4.3.1. Basics of Partition and Diffusion coefficients
VOCs and SVOCs emitted from solid surfaces (e.g., building materials, consumer products) can affect
indoor air quality (Cox et al., 2001). Because testing long-term emissions is costly and time-consuming,
mass transfer models have been developed to predict the emission and transport of chemicals. Initial
concentration in the source (C0), the solid-phase diffusion coefficient (Dm), material-air partition
coefficient (Kma), and gas-phase mass transfer coefficient (h) are key parameters that impact the
emissions. For new products and articles, C0 should be reported using Protocol 1: Source
Characterization. Parameter h is often estimated with empirical models. The partition and diffusion
coefficients are key to understanding the long-term effect of chemical emission from products and
articles.
Theoretically, the diffusion transport of molecules is related to the properties of the chemical, such as
molecular weight, molecular size (volume or area), molecular polarity, the properties of the substrate,
and environmental conditions, such as temperature, air velocity, and relative humidity. The material-air
partition coefficient is often correlated with the volatility of the chemical and properties of the
substrate. While there are many methods for experimental determination of Dm and Kma, standard
methods are lacking. No single method is suitable for testing all materials and chemicals. Most existing
methods are suitable for VOCs only.
4.3.2. Methods to Estimate Partition and Diffusion Coefficients
Table summarizes eight experimental methods for measuring the partition and diffusion coefficients for
solid materials. Details associated with each method are described below.
Table 5. Methods for Experimental Determination of Partition and Diffusion Coefficients.
Method
K
D
Applicability
Reference
Microbalance
Yes
Yes
VOCs
Cox et al., 2001
Zhao et al., 2004
No
Yes
VOCs
Meininghaus et al., 2002
Dynamic-static chamber
Yes
Yes
VOCs
He et al., 2010
Page 40
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Method
K
D
Applicability
Reference
Static diffusion metric
method
Yes
Yes
VOCs
Bodalal et al., 2001
Twin dynamic chamber
methods
Yes
Yes
VOCs
Xiong et al., 2009;
Xu et al., 2012
Meininghaus et al., 2000
Meininghaus et al., 2002
Dual chamber in series
Yes
Yes
SVOCs
Liu et al., 2014a, 2016
Variable volume loading
Yes
No
VOCs
Xiong et al., 2011
Cup method
No
Yes
VOCs
Kirchner et al., 1999
Porosity-based method
No
Yes
VOCs
Blondeau et al., 2003
4.3.3. Microbalance Method
The microbalance method can be used to estimate the partition and diffusion coefficients by placing the
test specimen on a microbalance located in a dynamic chamber with temperature and humidity control,
as shown in Figure (Cox et al., 2001; Zhao et al., 2004). In the beginning of the test, the sample weight is
first stabilized by passing clean air through the chamber until an equilibrium is obtained. The sorption
process begins by introducing an air stream with a constant and known concentration of VOC into the
chamber. The mass gain of the test specimen due to VOC sorption over time is monitored. The
monitoring continues for a period of time after the equilibrium is reached. During the desorption
process, the chamber is purged with clean air and the weight loss of the test specimen is monitored until
an equilibrium is re-established. This is a gravimetric method. With the sorption and desorption data
measured by the microbalance, the partition coefficient is determined by the ratio of the solid- and gas-
phase concentrations and the diffusion coefficient by non-linear regression.
Constant Temperature Enclosure
To
Exhaust ^
Hood
Micro-Balance
Sample
Chamber
Liquid/Air
Heat
Exchanger
Liquid
Temperature
Controller/
Circulator
Tare
Chamber
Diffusion Cell
Temperature
Transducer (RTD)
Cahn
Microbalance
Control and DAQ
PC
LabView
Parameter
Control and
DAQ PC
-Enclosure Temp
-Mass Flow
Figure 12. Schematic plot of the microbalance test system (Cox et al., 2001).
Page 41
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4.3.4. Dynamic-static Chamber Method
The system of the dynamic-static chamber method is composed of a FLEC, a static chamber (test
chamber), and a measurement device. One example of a measurement device is a proton transfer
reaction-mass spectrometer (PTR-MS) (Meininghaus et al., 2002; He et al., 2010). The static chamber
serves as a limited reservoir for gaseous VOCs. The test material, as a thin plate with uniform thickness,
is placed between the FLEC and the static chamber. During the test, clean gas (VOC free) from a
compressed air cylinder passes through the FLEC at a controlled rate (Figure 2), and VOC is introduced to
the static chamber at a certain concentration. The VOC in the static chamber will diffuse to the FLEC
through the test material driven by the concentration gradient. The real-time VOC concentration in the
outlet air of the FLEC is sampled and analyzed by an appropriate method. The concentration data is used
to estimate the partition and diffusion coefficients.
Mass flow controller
FLEC
By pass
PTR-MS
Barrier layer
Sampling port
Static chamber
2 Mixing fan
Carrier gas
Figure 23. Schematic plot of the dynamic-static chamber (He et al., 2010).
4.3.5. Static Diffusion Metric Method
The static diffusion metric method uses a twin static diffusion chamber system to determine the
diffusion coefficient (Bodalal et al., 2001). The testing material is installed between two chambers, and a
fan is installed in each chamber to mix the air (Figure 3). During the test, the VOC compound under
investigation is introduced into one chamber, while the initial concentration of the other chamber is
zero. Partition and diffusion coefficients are estimated based on a comparison of the measured gas-
phase concentrations in the two chambers.
i
Specimei
i/
Teflon Gasket
Membrane
V,.Ci
- specimen
SEE
_Sampling Port
High concentration chamber
Figure 34. Schematic plot of the diffusion metric method (Bodalal et al., 2001).
Page 42
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4.3.6. Twin Dynamic Chamber Method
The twin chamber method features two chambers separated by the test material. One chamber is dosed
with VOC through inlet air at a constant rate, while clean air passes through the other chamber. VOC
concentrations in both chambers are monitored continuously. Depending on the type of chamber used,
this method has several variations (Meininghaus et al., 2000, 2002; Xiong et al., 2009; Xu et al., 2012).
Figure 4 shows the generic test facility for the twin chamber method (Xiong el at., 2009). Different
methods are used to estimate the partition and diffusion coefficients from the experimental results.
Non-linear regression based on solutions to Fick's law is commonly used. The method proposed by Xiong
et al. (2009) takes into consideration the convective mass transfer although the calculation is somewhat
complex.
C2jn
material
chamber 2
fan
Cl.OI
Ci
C 2.
_JL_
~r
Cu
Cu
chamber 1
Figure 45. Schematic plot of the dual-chamber method (Xiong et al., 2009).
4.3.7. Dual Chamber in Series Method
The dual chamber in series method is a recently developed approach to estimate partition and diffusion
coefficients of SVOCs after solving issues, such as low concentrations in air, difficulty of measuring the
mass change, and strong sorption effects (Liu et al., 2014, 2016). The experiment setup is presented in
Figure 5, in which two environmental chambers are operated in series as the source and the material
test chambers. Outlet air from both chambers is measured by the polyurethane foam (PUF) samplers.
Test materials are pre-cleaned, punched into circular disks and are mounted on aluminum pin mounts
("buttons"), which are then placed on aluminum pin-mounted support blocks. Each chamber contains a
cooling fan to ensure the air is well-mixed. Prior to the experiment, the test chamber walls are pre-
coated with the SVOC to be investigated. During the tests, the material buttons are removed from the
test chamber at different exposure times to determine the amount of SVOC absorbed by the buttons
over time. Both partition and diffusion coefficients are estimated with a degree of sorption saturation
(DSS) model, which was originally developed by Deng et al. (2010), as the sorption saturation degree
(SSD) model.
Page 43
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Source Chamber
Test Chamber
Clean
Air
Sliced Caulk
s3 Fan
Sink Materials
Fan
PUF
PUF
Figure 56. Schematic plot of the dual chamber method (Liu et al., 2014).
4.3.8. Variable Volume Loading
The variable volume loading method (Xiong et al., 2011) uses a closed stainless steel chamber or a
sealable jar. The test specimen with known surface area and volume is placed in the chamber. Once the
equilibrium condition is reached, gas-phase concentration in the chamber is determined. The same
experimental procedure is repeated several times by changing the volume of the test specimen so the
loading factor is different from test to test. The initial concentration of the chemical in the test specimen
and material-air partition coefficient is estimated by plotting the equilibrium concentration versus the
ratio of the air volume over the volume of the test specimen.
4.3.9. Cup Method
This method determines the solid-phase diffusion
coefficient only. Based on an ISO 12572 on water vapor
diffusion (ISO, 2001), the cup method involves a cup of
liquid VOC at saturation in headspace. The top of the cup is
covered by a test specimen (Figure 6, Kirchner et al., 1999;
Blondeau et al., 2003). The system is placed in a
temperature and humidity-controlled environment, and the
diffusion coefficient of the tested specimen is estimated by
weighing the diffusion loss of VOC using a microbalance.
Bulk air phase
C*=0
Material
sample
Liquid VOC
Vi ฃV
Boundary
layer
Micro balance
4.3.10. Porosity-based Method
Diffusion coefficients can be estimated by the porosity-
based method through mercury intrusion porosimetry tests
(Blondeau et al., 2003). The first step is to conduct mercury
intrusion porosimetry (MIP) tests to characterize the porous
structure of the materials of interest, followed by applying Carniglia's mathematical model to estimate
the effective diffusivities of any gaseous species in these materials. Porosity-based method can be
applied to uniform, isotropic materials (properties are the same in all directions within the material).
Figure 67. Schematic plot of the cup method
(Blondeau et al., 2003).
4.4. Records Retention and Reporting Results:
4.4.1. Records to be Maintained
Records submitted to the EPA should include, but are not limited to, the following:
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a. The original signed protocol and any amendments.
b. Identification and characterization of the test substance as provided by Sponsor.
c. Identification and characterization of the material in question
d. Experiment initiation and termination dates.
e. Laboratory log books (e.g., stock solution concentration calculations and solution preparation,
calibration, and QC data).
f. Instrument (e.g., GC/ECNI) data files.
g. Spreadsheet files for data processing.
h. Environmental data acquired by the data acquisition system of the test chambers (e.g.,
temperature, air flow and inlet air moisture content).
i. Chain of custody documentation, including sample storage and handling information.
j. Copy of final report.
4.4.2. Final Report
A final report of the results of the study should be prepared and submitted to the EPA. The final report
should include, but is not limited to the following, when applicable:
a. Name and address of facility performing the study.
b. Dates on which the study was initiated and completed.
c. Objectives and procedures stated in the approved protocol, including any changes in the original
protocol.
d. Identification and characterization of the test substance as provided by Sponsor.
e. A summary and analysis of the data and a statement of the conclusions drawn from the analysis.
f. A description of the transformations and calculations performed on the data.
g. A description of the methods used and reference to any standard method employed.
h. A description of the instrumentation utilized.
i. A description of the preparation of the test solutions, the test conditions, the testing
concentrations, and the duration of the test.
j. A description of sampling and analytical methods, including level of detection, level of
quantification, and references.
k. A description of test specimens and test matrix.
I. A description of the test results including measured values for individual chemicals of interest
for each matrix.
m. A description of all circumstances that may affect the quality or integrity of the data.
n. The name of the study director, the names of other scientists or professionals, and the names of
all supervisory personnel involved in the study.
o. The signed and dated reports of each of the individual scientists or other professionals involved
in the study, if applicable.
p. The location where the raw data and final report are to be stored.
q. A statement prepared by the Quality Assurance Unit listing the types of inspections, the dates
that the study inspections were made, a description of quality assurance and quality control
process, and the findings reported to the Study Director and Management.
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r. A copy of all raw data including but not limited to instrumentation output, lab notebooks, and
data sheets, etc.
4.5. References:
Blondeau, P., A. Tiffonnet, A. Damian, O. Amiri and J. Molina (2003). Assessment of Contaminant
Diffusivities in Building Materials from Porosimetry Tests. Indoor Air 13(3): 310-318.
Bodalal, A., Plett, E.G., Zhang, J.S., and C. Y. Shaw, C. Y. (2001). Correlations Between the Internal
Diffusion and Equilibrium Partition Coefficients of Volatile Organic Compounds (VOCs) in Building
Materials and the VOC Properties. ASHRAE Transactions, 107, (Part l):789-800.
Cox, S. S., D. Zhao and J. C. Little (2001). Measuring Partition and Diffusion Coefficients for Volatile
Organic Compounds in Vinyl Flooring. Atmospheric Environment, 35(22): 3823-3830.
Deng, Q., X. Yang and J. S. Zhang (2010). New Indices to Evaluate Volatile Organic Compound Sorption
Capacity of Building Materials (Rp-1321). HVAC&R Research, 16(1): 95-105.
He, Z., W. Wei and Y. Zhang (2010). DynamicStatic Chamber Method for Simultaneous Measurement
of the Diffusion and Partition Coefficients of VOCs in Barrier Layers of Building Materials. Indoor and
Built Environment, 19(4): 465-475.
ISO (2001). BS EN ISO 12572: 2001, Hygrothermal Performance of Building Materials and Products.
Determination of Water Vapor Transmission Properties,"
Kirchner, S., J. Badey, H. N. Knudsen, R. Meininghaus, D. Quenard, H. Sallee and A. Saarinen (1999).
Sorption Capacities and Diffusion Coefficients of Indoor Surface Materials Exposed to VOCs.
Proposal of New Test Procedures. Indoor Air 99.
Liu, X., Z. Guo and N. F. Roache (2014). Experimental Method Development for Estimating Solid-Phase
Diffusion Coefficients and Material/Air Partition Coefficients of SVOCs. Atmospheric Environment,
89: 76-84.
Liu, X., Allen, M. R., Roache, N. F. (2016). Characterization of Organophosphorus Flame Retardants'
Sorption on Building Materials and Consumer Products. Atmospheric Environment, 140: 333-341.
Meininghaus, R., L. Gunnarsen and H. N. Knudsen (2000). Diffusion and Sorption of Volatile Organic
Compounds in Building Materials-Impact on Indoor Air Quality. Environmental Science & Technology,
34(15): 3101-3108.
Meininghaus, R. and E. Uhde (2002). Diffusion Studies of VOC Mixtures in a Building Material. Indoor Air,
12(4): 215-222.
Xiong, J., Y. Zhang, W. Yan and Z. He (2009). An Improvement for Dynamic Twin Chamber Method to
Measure VOC Diffusion Coefficient and Partition Coefficient. ASHRAE Transactions 115(2).
Xiong, J., W. Yan and Y. Zhang (2011). Variable Volume Loading Method: A Convenient and Rapid
Method for Measuring the Initial Emittable Concentration and Partition Coefficient of Formaldehyde
and Other Aldehydes in Building Materials. Environmental Science & Technology, 45(23): 10111-
10116.
Xu, J., J. S. Zhang, X. Liu and Z. Gao (2012). Determination of Partition and Diffusion Coefficients of
Formaldehyde in Selected Building Materials and Impact of Relative Humidity. Journal of the Air &
Waste Management Association, 62(6): 671-679.
Zhao, D., J. C. Little and S. S. Cox (2004). Characterizing Polyurethane Foam as a Sink for or Source of
Volatile Organic Compounds in Indoor Air. Journal of Environmental Engineering, 130(9): 983-989.
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5. Particulate Matter Formation Due to Mechanical Forces Applied to Product
or Article Surfaces
5.1. Purpose:
The objective of this protocol is to determine how much particulate matter is formed due to mechanical
forces (abrasion) applied to the surface of a product or article under simulated conditions designed to
mimic routine use over the lifecycle of a product.
5.2. Modifications:
This protocol is general, and it is anticipated that during protocol development and finalization,
additional modifications will be made to tailor the sampling parameters or analytical techniques to the
specific chemical and product tested, as well as to Agency recommendations specific to particular
products, chemicals, or exposure scenarios of interest.
5.3. Description:
5.3.1. Approach
Particulate matter (PM), suspended or settled, plays an important role in human exposure to chemicals
in the indoor environment. There are three major mechanisms by which chemicals in products or
articles may transfer to particles: particle/air partitioning (sorption of vapor), particle/solid material
partitioning (migration by direct contact), and particle formation due to weathering or mechanical
forces, such as abrasion applied to the source (e.g., flaking and chalking). This document describes a
generic protocol for testing particle formation due to abrasion. The design concept of this method is
based on ISO 9073-10 (ISO, 2003), ASTM G195-13a (ASTM, 2013) and Morgeneyer et al. (2015). The
abrasion test is conducted using a rotary platform abraser placed in a flow-through test chamber.
Particle concentration in the chamber is monitored continuously using a particle counter capable of
measuring particles in the range of 0.3 to 25 urn in diameter. The test results are used to calculate the
particle generation rate and abrasion index. In addition, large particles and debris that fall to the floor
from the abraser are collected with a micro-vacuum dust sampler. The mass of collected dust is
quantified for two size fractions: fine dust (diameter < 50 urn) and coarse dust (diameter > 50 urn).
5.3.2. Test Facility and Apparatus
The test facility, as shown in Figure 18, is based on the principles described in ISO 9073-10 (ISO, 2004)
and Morgeneyer et al. (2015) with modifications. It consists of the rotary platform abraser, test chamber
system, and particle counter.
Page 47
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Filter
Pump
Conditioned Air
Fan
Test Chamber
Filter
r
\braser
/
Tabe
Exhaust
Particle
Counter
Figure 78. Schematic of the test facility for particle generation due to abrasion.
5.3.2.1. Abrasion Apparatus
Many standard abrasion test methods are available. In this generic protocol, the rotary platform
abrasion method described in ASTM G195 (ASTM, 2013), also known as the Taber abrasion method, is
chosen because it can be applied to a wide range of products/articles. There are over 100 standard
methods for Taber abrasion tests alone. Selection of a proper method depends on the type of material
to be tested although the basic principles are the same.
5.3.2.2. Test Chamber
The test chamber is an air-tight enclosure with air flow, temperature, and humidity controls. It is used to
house the abrasion apparatus and provide a well-mixed air space from which air samples can be drawn
for particle counting. Typical operating conditions of the chamber are 0.5 to 1 air change per hour, 23 to
25 ฐC, 50% relative humidity, and approximately 0.1 m/s air speed. Although several types of enclosures
can serve as the test chamber for testing particle generation, large stainless steel chambers (ASTM
D6670) are preferred as they can meet all the aforementioned requirements. A chamber with a volume
of roughly 10 m3 is ideal.
5.3.2.3. Particle Counters
Particle counters are used to determine the number concentration and size distribution of airborne
particles. In this protocol, the particle counter should have at least 8 size bins (channels) that must
cover the range of aerodynamic diameters from 0.3 to 25 nm. If a single particle counter cannot cover
this range, two particle counters with different size ranges can be used. Furthermore, the particle
counter should have a sampling frequency of at least once per minute.
5.3.2.4. Micro Vacuum Dust Sampler
The floor dust sampler is used to collect large particles and debris from the chamber floor generated by
abrasion. It should meet the specifications of either ASTM 5438 (ASTM, 2011) or ASTM 7144 (ASTM,
2016).
Page 48
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5.3.2.5. Other Equipment and Devices
A micro balance with a readability of 0.1 mg or better is needed for weighing the dust samples collected
by the micro vacuum dust sampler. A stainless steel mesh sieve with a diameter of 8 in. (20.3 cm) and
U.S. mesh size 270 is needed for dividing the dust into fine and coarse fractions.
5.3.3. Preparations
5.3.3.1. Preparation of the Test Articles
The test article should have a flat surface and be clean. Typical article size is 100 mm x 100 mm square
with a 6.5 mm hole at the center. Flexible materials are typically cut into 100 mm-diameter disk with a
6.5 mm hole at the center. The thickness of the test specimens should be no greater than 6.35 mm. A
mounting card may be needed for certain flexible specimens that may wrinkle or shift during testing. For
each material to be tested, a minimum of five disks should be prepared.
To determine the background emissions of particles due to the operation of the abraser without test
articles, polished stainless steel disks should be prepared according to the dimensions mentioned above.
5.3.3.2. Preparation of the Test Chamber
Before testing, the chamber floor, ceiling and walls should be cleaned with a vacuum cleaner equipped
with a HEPA filter and then wiped cleaned with wet cloth.
5 .3.3.3. Preparation of the Abrading Wheel
Many types of abrasive wheels are commercially available. To standardize the test condition and
maximize the comparability of the test results, Taber abrading wheel type CS-10W
(http://www.taberindustries.com/taber-abrading-wheels) or equivalent should be used. This type of
wheel provides mild to medium abrading action depending on the abrading wheel loading.
5.3.3.4. Abrading Wheel Loading
Selection of abrading wheel loading in conventional abrasion tests is aimed to permit a minimum
number of abrasion cycles (e.g., 150). A mass of 500 or 1000 g per wheel is recommended for durable
materials and 250 or 500 g per wheel for less durable materials. Because this protocol requires longer
abrasion durations (at least 30 min) for particle sampling purposes, an abrading wheel loading of 250 g
per wheel is recommended for all materials. Tests should use the same type of abrading wheel and
wheel loading to allow for direct comparison of test results.
5.3.3.5, Suction System
Commercially available rotary platform abraders are equipped with a vacuum suction system for
removing debris and abrading particles during testing. The exhaust of this suction system should be
pointed at the center of the chamber at a roughly 45ฐ angle of elevation to allow the particles to
disperse in the chamber.
5.3.4. Generic Test Procedure
5.3.4.1. Background Tests
Operating the abraser itself may generate a small amount of particles from the motor (Morgeneyer et
al., 2015). This background test allows characterization of the background particle emissions. The test
results are used to calculate the background particle generation rate, which will be excluded from the
test results for the test article. The test procedure is as follows.
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a. Set chamber temperature at 25ฐ C, relative humidity at 50%, and ventilation rate at 0.5 air
change per hour. Turn on the mixing fan. Allow the chamber conditions to stabilize.
b. Turn on the particle counter.
c. Continue to monitor the particle concentrations in the chamber for 1 hour. The particle
concentrations measured represent the chamber background without the operation of the
abraser.
d. Mount the CS-10F abrasive wheels; select the abrading wheel loading (250 g); set the turntable
speed at 60 rpm.
e. Mount the polished stainless steel disk on the turntable.
f. Secure test specimen according to ASTM G195-13a, Sections 11.3.1 and 11.3.2 (ASTM, 2013).
g. Turn on the abraser and run the test for 1 hour. The particle concentrations measured represent
the chamber background with the operation of the abraser.
h. Turn off the abraser; record abrasion test stop time.
i. Continue to monitor the particle concentrations in the chamber for at least 30 more min.
j. Turn off the particle counter; record the test finish time.
5.3.4.2. Sample Abrasion Test
The procedure for testing material samples is the same as that for the background test except that the
polished stainless steel disks are replaced by the test article disk. If the sample abrasion is conducted
immediately after the background test, there is no need to determine the chamber background without
an operating rotary platform abraser. Note that, for articles with different materials on each side (e.g.
wood panel with one side laminated), the side exposed to air and thus, the consumer, in the
product/article should be tested.
5.3.4.3. Floor Dust Collection
This step is needed only if the abrasion test generates large particles and debris that fall on the chamber
floor.
a. Open the chamber door after sample abrasion test is complete.
b. Use the micro vacuum dust sampler to collect dust and debris from chamber floor according to
ASTM 5438 (ASTM, 2011) or ASTM 7144 (ASTM, 2016).
c. After dust collection, divide the dust collected from the bag into two fractions with the No. 270
sieve.
d. Transfer each of the two fractions into a pre-weighed weigh boat to determine the dust weight.
5.3.5. Calculations
5.3.5.1. Aerosol Particle Generation Rate
Use the first hour data to calculate the aerosol particle generation rate. Equation 5-1 is applicable to the
particle generation rate for both background and abrasion tests.
Gi = Nlout+Nj+Nld
where Gl = particle generation rate for the i size bin (particles/h)
^ -
*out
Nlout = number of particles in the ith size bin that leaves the chamber, calculated from Equation
5-2
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N{ = number of particles in the ith size bin remaining in the chamber by the end of test
duration, calculated from Equation 5-3
Nld = number of particles in the ith size bin deposited onto chamber walls during the test
duration, calculated from Equation 5-4
t = test duration, in hours
Kut = Qclt (5-2)
Ni = Vcl (5-3)
N>= Vk^c't (5-4)
where Q = ventilation flow rate of the chamber (m3/h)
cl = average particle number concentration in the ith size bin during the test duration while the
abraser is on (particles/m3)
V = chamber volume (m3)
clt = particle number concentration in the ith size bin at the end of test duration while the
abraser is on (particles/m3)
kld = first-order deposition rate constant for particles in the ith size bin (h_1)
Note that the first-order deposition rate constants are size dependent. They can be determined by the
experimental data (see the Appendix 5-A). If they cannot be determined experimentally (e.g., the
particle counts are too close to the chamber background levels), use kld = 0.6 (h_1) for all size bins.
5.3.5.2. Particle Generation Rate due to Abrasion of Test Specimen
The particle generation rate due to abrasion of test specimen is calculated from Equation 5-5:
Gj = Gls- GlB (5-5)
Where G\ = particle generation rate for the ith size bin due to abrasion (particles/h)
G$ = particle generation rate for the ith size bin determined by abrasion test and Equation 5-1
(particles/h)
Gg = particle generation rate for the ith size bin determined by background test and Equation 5-1
(particles/h)
5.3.5.3. Abrasion Index
The abrasion index is defined by Equation 9, which is similar to the coefficient of linting as defined in BS
EN ISO 9073-10 (ISO, 2003).
/j = log(Gj) (5-6)
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Where I\ = abrasion index for particles in the ith size bin.
5.3.6. Replicate Tests
For a given material, five tests should be conducted with five separate disks. The test results (i.e.,
particle generation rate and abrasion index) should be reported as mean ฑ standard deviation.
5.3.7. Safety Issue
It is highly recommended the abrasion apparatus be operated remotely outside the test chamber. If the
operator should be inside the chamber during the test, a safety and health plan should be developed
and implemented.
5.4. Records Retention and Reporting Results:
5.4.1. Records to be Maintained
Records submitted to the EPA should include, but are not limited to, the following:
a. The original signed protocol and any amendments.
b. Identification and characterization of the test substance as provided by Sponsor.
c. Identification and characterization of the material in question
d. Experiment initiation and termination dates.
e. Laboratory log books (e.g., stock solution concentration calculations and solution preparation,
calibration, and QC data).
f. Instrument (e.g., GC/ECNI) data files.
g. Spreadsheet files for data processing.
h. Environmental data acquired by the data acquisition system of the test chambers (e.g.,
temperature, air flow and inlet air moisture content).
i. Chain of custody documentation, including sample storage and handling information,
j. Copy of final report.
5.4.2 Final Report
A final report should be prepared, and records should be retained in accordance with 40 CFR 792,
Subpart J - Records and Reports. For example, the following key information should be included in the
report:
a. Test material: material name, intended use, uniformity (homogeneous, layered, spray
application, coating, etc.), and dimensions of test specimens. If the two sides of the material are
different, indicate which side is tested.
b. Abrasion apparatus: abrader brand and model number, abrading type (abrasive characteristics
of the wheel), and operating parameters.
c. Test chamber: chamber brand and model number, volume, dimensions, and interior surface
material.
d. Environmental conditions: chamber air flow rate, temperature, relative humidity, and air speed
expressed in arithmetic mean and standard deviation.
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e. Particle counters: particle counter type, brand, and model number.
f. Test procedure: description or citation, including deviation from standard procedure.
g. Test results: particle counts vs time for each size bin and sampling air flow; gravimetric data for
fine and coarse fractions of dust and debris.
h. Calculated results: particle-size specific generation rates (from Equation 8) and abrasion indices
(from Equation 9) for individual tests plus mean and standard deviation for replicate tests.
5.5. References:
ASTM 6670-01 (2007) Standard Practice for Full-Scale Chamber Determination of Volatile Organic
Emissions from Indoor Materials/Products, available at http://www.astm.org/Standards/D6670.htm
ASTM D5438 -11 (2011) Standard Practice for Collection of Floor Dust for Chemical Analysis.
https://www.astm.org/Standards/D5438.htm
ASTM (2013). G195 - 13a Standard Guide for Conducting Wear Tests Using a Rotary Platform Abraser
ASTM (2016). D7144-05 Standard Practice for Collection of Surface Dust by Micro-vacuum Sampling
for Subsequent Metals Determination. https://www.astm.org/Standards/D7144.htm
ISO (2003).BS EN ISO 9073-10. Lint and other particles generation in the dry state. Available at
http://shop.bsigroup.com/ProductDetail/?pid=OOOOQ0000030099719
Morgeneyer, M., Shandilya, N., Chen, Y.M., Bihan, O.L. (2015). Use of a Modified Taber Abrasion
Apparatus for Investigating the Complete Stress State during Abrasion and in-process Wear Particle
Aerosol Generation, Chemical Engineering Research and Design, 93:251-256.
Page 53
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Appendix 5A. Estimation of the First-Order Deposition Rate Constant using
Experimental Data
If the particle generation rate due to abrasion is roughly constant, the measured particle number
concentration profile is expected to resemble that in Figure 19.
1000
SOO
3 600
O
(J
V
J
t 400
CT5
CL
200 '
0
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2
Elapsed Time (h)
Figure 19. Expected particle count profile during an abrasion test. The data collected after the abraser stops is
used to estimate the deposition rate constant.
Using the decay data (i.e., the data between 1 and 1.5 elapsed hours in Figure 19), the first-order
deposition rate constant can be estimated as follows:
i. Plot the number concentration decay data on a semi-log scale (Figure 20).
j. Calculate the slope of the line from the plot
k. Calculate the first-order deposition rate constant from Equation 5A-1.
(5A-1)
Where kld = the first-order deposition rate constant for the ith size bin (h_1)
|S'| = absolute value of the slope obtained from the the plot (h1)
Nv = chamber ventilation rate (h1).
Abraser stops
Page 54
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1000
+J
C
3
O
u
(D
U
'+-ป
03
Q_
100
1.1 1.2 1.3 1.4 1.5
Elapsed Time (h)
Figure 20. Semi-log plot for particle count versus time during the decay phase (i.e.,
flushing the chamber).
Page 55
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6. Direct Transfer of Chemicals from Source to Settled Dust
6.1. Purpose:
The objective of this protocol is to characterize the rate of chemical migration from a product or article
to settled dust that is in direct contact with product or article, and to semi-quantitatively or qualitatively
determine if gas-phase transfer plays a role in chemical transfer from consumer articles to settled dust.
6.2. Modifications:
This protocol is general, and it is anticipated that during protocol development and finalization,
additional modifications will be made to tailor the sampling parameters or analytical techniques to the
specific chemical and product tested, as well as to Agency recommendations specific to particular
products, chemicals, or exposure scenarios of interest.
6.3. Description:
Tests should be conducted in standard environmental chambers where indoor conditions (temperature,
humidity, etc.) can be simulated in a controlled manner. Similar tests involving chemical transfer to
house dust particles have been conducted in FLEC (Jeon et al., 2016; Clausen et al., 2004), micro
chambers (Liagkouridis et al. 2017), small chambers (Clausen et al., 2004), and large chambers (Liu et al.,
2016). Small or mid-sized chambers are recommended for this protocol because of their availability,
cost-effectiveness, and ease of cleaning.
The general steps of the protocol for a mid-sized or large chamber are as follows:
a) Cut panels from the consumer article (article panel) to be tested.
b) Prepare stainless steel plates or aluminum foil sheets which will be used to determine
whether vapor phase transfer plays a role in migration of the chemical of interest from
source to settled dust.
c) Apply National Institute of Standards and Technology (NIST) Standard house dust, free of
chemical of interest, evenly to the surface of each article panel or stainless steel plate.
d) Conduct tests at four dust loading levels to investigate the effect of dust loading on transfer
rate.
e) Place the dust laden article panels and stainless steel plates or aluminum foil sheets into the
environmental chambers for the aging test under typical indoor environmental conditions.
f) Place polyurethane foam (PUF) passive air samplers inside the chamber to collect integrated
air samples for vapor-phase chemicals of interest.
g) Remove the dust laden article panels and stainless steel plates or aluminum foil sheets from
the chambers at different elapsed times over the sampling period as specified by the
experimental schedule (Table 6).
h) Collect dust samples from the article panels and stainless steel plates or aluminum foil
sheets, extract and analyze dust samples for chemicals of interest.
i) Collect PUF air samples, extract and analyze for chemicals of interest. Note, the air sampling
portions of this protocol may be waived if the measured vapor pressure of the chemical of
interest is shown to be below the method detection limit.
Four tests should be conducted for each article according to Table 6.
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Table 6. Example Experimental Schedule.
Test ID
Dust loading
(g/m2)
Dust panel type
Number of
panels3
Panel removal schedule
(elapsed days)
1
Article panel
12
1, 5,10,15, 20, 30
Stainless steel plate
6
3, 15, 30
2
Article panel
12
1, 5, 10, 15, 20, 30
Stainless steel plate
6
3, 15, 30
3
on
Article panel
12
1, 5, 10, 15, 20, 30
zU
Stainless steel plate
6
3, 15, 30
4
Article panel
12
1, 5, 10, 15, 20, 30
bU
Stainless steel plate
6
3, 15, 30
a: the number of panels is related to the size of the chamber and can vary
6.3.1. Materials and Equipment
The following procedure should be followed for preparing test specimens for consumer articles
containing the chemical of interest:
a) For the test results to be meaningful, the initial concentration of the chemical of interest in
the article should be reported (for example, see Protocol 1: Source Characterization.)
b) Cut the test specimens into 22 cm by 20 cm or other appropriately sized panels. The bottom
of the test chamber should be able to accommodate at least two panels.
c) The thickness of the article panel depends on the article type and should be easy to handle.
In general, a thickness of 5 mm is adequate for most articles except fabrics and other thin
materials, which should be tested with their original thicknesses. Foam articles can be
thicker.
d) Clean the article panels on all exposed sides with a hand-held vacuum cleaner to remove
debris and particles formed during the cutting process, minimizing interference with test
results.
e) Prepare a total of 14 Article panels, including 2 as back-ups, for each test. Wrap the
prepared article panels in two layers of aluminum foil and store at room temperature.
NIST house dust standard reference material SRM 2585 (NIST house dust), free of target compounds, is
recommended for this test method (NIST, 2014). The key properties of the dust that should be reported
include:
Dust density,
Organic carbon (OC) content, and
Aerodynamic particle size distribution (e.g., geometric mean and geometric standard
deviation).
The standard dust should be extracted and analyzed for background chemical of interest contents prior
to product testing, according to the best analytical methods available.
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Tests are conducted in small environmental chambers constructed and operated according to ASTM
D5116, Standard Guide for Small-Scale Environmental Chamber Determinations of Organic Emissions
from Indoor Materials/Products (ASTM, 2010). Chambers with volumes between 50 and 200 L are
suitable for this test method. The suggested chamber operating conditions are listed in Table 7. Record
and report actual chamber operating conditions.
Table 7. Operating Conditions of Small Test Chambers for Testing Migration of Chemical of Interest from Source
Article to Dust.
Parameter
Condition
Notes
Air supply
Filtered, humidified clean air
Air change rate
1 per hour
Temperature
23 ฐC
[a]
Relative humidity
50%
Air speed of chamber air
5 to 10 cm/s
[b]
aTest chambers are housed in an incubator for temperature control.
bThe air speed may be measured with a calibrated hotwire anemometer in an empty test chamber, 1 cm above the
center of the chamber bottom. Replacing the stainless steel chamber lid with a transparent plastic one allows
visual adjustment of the probe's location.
Modifications may be made to standard small chambers tests. For example, metal racks could be used
to accommodate more article panels. The number of panels is related to the chamber size selected.
Additional laboratory apparatus and supplies that will be necessary for the testing include:
a) Microbalance with a capacity of 50 g and readability of 0.1 mg
b) 8" stainless steel sieves with 250 and 125 urn hole sizes
c) Stainless steel micro spatulas with spooned end
d) Aluminum foil with a thickness of 2 mils (~51 urn) for sample storage
e) Aluminum foil with a thickness of 4 mils (~102 urn) for dust collection
f) Amber glass scintillation vials (20 mL of volume, 28 mm x 61 mm in size, and with screwed
cap) for collecting and extracting dust samples
g) 20 Gauge (0.9 mm) stainless steel plates (24 cm by 24 cm) for creating blank dust panels
h) PUF disks (14 cm in diameter and 1.5 cm in thickness) for passive air sampling inside the
chambers
6.3.2. Methods
6.3.2.1. General Procedure
Test chamber preparation:
Clean the test chamber prior to each test by wiping all of the interior surfaces with isopropyl
alcohol wipes followed by washing with water and detergent.
Set to an inlet air flow rate of 1ACH and 50% relative humidity via the data acquisition
system. Set the incubator temperature at 23 ฐC.
Run the empty chambers for a minimum of 8 hours to clean the chamber with clean air.
Take a background air sample to ensure that the chamber is free of contamination.
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Apply NIST house dust to the article panels prior to the chamber test. Four known amounts of NIST
house dust are spread onto a known surface area of the article panel as evenly as possible. The
recommended NIST house dust loadings per panel or plate are 10, 20, 40, and 60 g/m2. Report the
amount of dust spread onto the surface in g/m2.
Use the following steps to load dust onto the article panels and stainless steel plates.
a) Unwrap the article panel or select a stainless steel plate or aluminum foil sheet, and place it
on the table of the fume hood.
b) Place the 125 urn sieve on the panel or plate and then place the 250 urn sieve on top of the
125 urn sieve.
c) Use the micro spatula with a spooned end to transfer a desired amount of dust from the vial
to the mesh of the top sieve as evenly as possible by slowly moving the spoon while gently
tapping the rod of the spoon/spatula with a finger.
d) Use the 10-mm flat art paintbrush to gently push or drag the dust on the mesh in a circular
motion; continue this process until all dust particles fall through the top sieve.
e) Lift the top sieve slowly.
f) Use the 10-mm flat art paintbrush to gently push the dust on the bottom sieve on different
directions; continue this process until all dust particles fall through the sieve.
g) Lift the bottom sieve slowly.
h) Calculate the dust loading by dividing the amount of dust applied by the area of the sieve
screen. For example, if 1 g of dust is applied and the inside diameter of the screen is 7" (17.8
cm), the dust loading is approximately 40 g/m2.
i) Report the four dust loadings applied to each panel or plate.
Note that these steps for dust loading need practice. If the dust particles fall through the mesh either
too slowly or too rapidly, a different combination of screen sizes (e.g., two 250-nm or two 125-n sieves)
may be considered. To reduce cost, it is recommended that house dust collected from vacuum cleaner
bags and processed according to the certificate of the NIST standard house dust be used for this practice
(NIST, 2014). Briefly, the house dust collected is sterilized and then screened first through a 250 urn
sieve and then a 100 urn sieve.
The chamber test can be conducted through the directions below. Throughout the test, environmental
conditions (temperature, relative humidity, and air flow) of the chamber should be monitored and
recorded continuously.
a) Open chamber lid.
b) For the large chamber test, use removable, two-sided tape to mount two PUF disks onto the
back wall of the chamber at half height.
c) Place the 12 dust loaded article panels and 6 loaded stainless steel panels or aluminum foil
sheets per dust loading level into chambers, on chamber floors and racks.
d) Close the chamber and record the test start time.
e) Remove two article panels at each of the following elapsed days: 1, 5,10, 15, 20, and 30.
f) Remove two stainless steel plates or aluminum foil sheets at each of the following elapsed
days: 5, 15, and 30.
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g) Collect dust samples from article panels and stainless steel plates or aluminum foil sheets
according to the chamber test directions above.
h) Extract and analyze dust samples according to the dust extraction and purification, and
sample analysis described below in section 6.3.3, Sample Extraction and Analysis.
i) Remove the two PUF disks after the last set of panels are removed on the 30th elapsed day;
extract them separately according to the best available method(s) of PUF disk sample
extraction and purification for the test chemical of interest.
6.3.2.2. Collection of Dust Samples
Collection of the NIST house dust from article panels and stainless steel plates or aluminum foil sheets is
conducted according to the following directions. Dust collection should be conducted in a fume hood
with a low air speed to ensure that the dust in not inadvertently blown away during dust collection by a
strong air draft.
a) Store the scintillation vials used for collecting dust samples in a desiccator for at least 8
hours and pre-weighed prior to sample collection.
b) Place a 30 cm by 30 cm sheet 4-mil aluminum foil on the table of the fume hood.
c) Hold the test panel removed from the chamber horizontally with both hands; Move the
panel over the aluminum foil.
d) Slowly turn the test panel to vertical position with one side of the panel touching the foil
(Figure 21).
e) Use one hand to hold the panel while gently tapping the back of the panel with a spatula to
allow the dust particles to fall onto the aluminum sheet.
f) Tilt the test panel slightly such that its side with dust and table surface form an angle of
approximately 80ฐ (Figure ). Continue to tap the back of the panel until most dust particles
fall on the aluminum sheet.
g) Remove the test panel from which dust has been removed.
h) Fold the aluminum foil to form a U shape; hold the folded aluminum foil with one hand and
use a spatula to tap the outside of the folded panel to allow the dust to settle on the bottom
of the U-shaped foil sheet (Figure 8).
i) Place the folded aluminum sheet aside inside the fume hood; place a new piece of
aluminum foil (roughly 30 cm x 30 cm) on the table.
j) Place a centrifuge tube holder on the aluminum foil.
k) Place a 20-mL scintillation vial in the tube holder (Figure ).
I) To transfer the collected dust into the pre-weighed scintillation vial, tilt the folded
aluminum foil sheet to about 45ฐ to allow the dust to "flow" into the scintillation vial (Figure
23); tap the panel gently with a spatula if necessary.
m) Weigh the sample vials immediately. Record the weight of the dust sample in grams to at
least four significant figures.
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Dust-laden pane!
(with a 80ฐ angle)
Dust-laden panel
(in vertical position)
Aluminum foil
Figure 21. Collecting dust from test panels by placing the panel on the 4-mil-thick aluminum foil
vertically (left) and then tilt it further towards the dust-laden side to form an approximately 80ฐ
angle with the aluminum foil. Use the spatula rod to tap the hack of the panel in both positions.
Figure 82. The dust particles form a line after the aluminum sheet is folded into the U shape.
The unfolded panel shown in this picture is a thin aluminum plate instead of 4-mil aluminum
foil.
Figure 23. Dust sample is transferred from folded aluminum sheet to the scintillation vial.
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Note that it is not required to collect 100% of the dust from the test panels because the chemical
content in the dust is determined on a weight per weight basis (e.g., ng chemical/g dust). Dust collection
efficiency should be in the range of at least 50% of dust transferred to scintillation vial.
633. Sample Extraction and Analysis
See Section 3.3.7 Sample Extraction and Analysis under Protocol 3.
6.4. Records Retention and Reporting Results:
6.4.1. Records to be Maintained
Records submitted to the EPA should include, but are not limited to, the following:
a. The original signed protocol and any amendments.
b. Identification and characterization of the test substance as provided by Sponsor.
c. Identification and characterization of the material in question
d. Experiment initiation and termination dates.
e. Laboratory log books (e.g., stock solution concentration calculations and solution preparation,
calibration, and QC data).
f. Instrument (e.g., GC/ECNI) data files.
g. Spreadsheet files for data processing.
h. Environmental data acquired by the data acquisition system of the test chambers (e.g.,
temperature, air flow and inlet air moisture content).
i. Chain of custody documentation, including sample storage and handling information,
j. Copy of final report.
6.4.2. Final Report
A final report should be prepared, and records should be retained in accordance with 40 CFR 792,
Subpart J - Records and Reports.
The standard test methods mentioned above contain sections for reporting. For example, key
information to be reported includes:
a. Test material: material name, intended use, uniformity (homogeneous, layered, spray
application, coating, etc.), dimensions of test specimens, exposed area, treatment of sample
edges (sealed or exposed) and information about sample creation, transport, and storage (See
Contextualizing Information for Product Use).
b. Target chemical(s) and their basic properties: CAS number, molecular formula, vapor pressure,
chemical reactivity, concentration in material, etc. (See Contextualizing Information for Product
Use).
c. Test chamber: chamber type, model name, volume, dimensions, and interior surface material.
d. Test procedure: description or citation, including deviation from standard procedure.
e. Sampling methods for air and dust samples and analytical methods description or citation,
including deviation from standard procedure. Description of accuracy and precision
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f. Analytical methods: description or citation, including deviation from standard procedure.
g. Environmental conditions: chamber temperature (expressed in arithmetic mean and standard
deviation) and moisture content in cooling air.
h. Test results: chromatograms of air and dust samples, identification of peaks, time-averaged
concentrations in chamber air from static air sampler and dust samples.
i. QA/QC data: accuracy and precision of measurements, calibrations, daily calibration checks,
background samples, blank samples.
6.5. References:
ASTM. (2010). D5116-10 Standard Guide for Small-scale Environmental Chamber Determinations of
Organic Emissions from Indoor Materials/Products. http://www.astm.org/Standards/D5116.htm.
Clausen, P; Hansen, V; Gunnarsen, L; Afshari, A; Wolkoff, P. (2004). Emission of Di-2-ethylhexyl phthalate
from PVC Flooring into Air and Uptake in Dust: Emission and Sorption Experiments in FLEC and
CLIMPAQ. Environmental Science & Technology, 38: 2531-2537.
http://www.ncbi.nlm.nih.gov/pubmed/15180047.
Jeon, S; Kim, KT; Choi, K. (2016). Migration of DEHP and DINP into Dust from PVC Flooring Products at
Different Surface Temperature. The Science of the Total Environment, 547: 441-446.
http://www.ncbi.nlm.nih.gov/pubmed/26824397.
Liagkouridis, I., Lazarov, B., Giovanoulis, G., & Cousins, I. T. (2017). Mass transfer of an organophosphate
flame retardant between product source and dust in direct contact. Emerging Contaminants.
http://www.sciencedirect.com/science/article/pii/S2405665017300173
Liu, X; Guo, Z; Krebs, KA; Greenwell, DJ; Roache, NF; Stinson, RA; Nardin, JA; Pope, RH. (2016).
Laboratory Study of PCB Transport from Primary Sources to Settled Dust. Chemosphere, 149: 62-69.
http://www.ncbi.nlm.nih.gov/pubmed/26849196.
NIST (2014). Certificate of Analysis Standard Reference Material #2585 (pp. 1-13). (SRM 2585).
Gaithersburg, MD: National Institute of Standards & Technology. https://www-
s. nist.gov/srmors/certifi cates/2585.pdf?CFI D=43597555&CFTQKEN=bd713ff0f9f0bl05-7D32F184-
0FD5-F338-8C2F0D7ECCA435D2.
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7. Photolysis under Simulated Indoor Lighting Conditions
7.1. Purpose:
The objective of this protocol is to determine whether a chemical in a product or article is subject to
photolytic degradation under simulated indoor lighting conditions and what the major degradation
products are. If the chemical was found in appreciable concentrations in house dust from Protocol 6,
then this protocol should be followed.
7.2. Modifications:
This protocol is general, and it is anticipated that during protocol development and finalization,
additional modifications will be made to tailor the sampling parameters or analytical techniques to the
specific chemical and product tested, as well as to Agency recommendations specific to particular
products, chemicals, or exposure scenarios of interest
7.3. Description:
7.3.1. Approach
Photolysis, or photolytic degradation, is a chemical reaction by which the compound is broken down by
light (photons). This process is relevant to indoor environmental quality and human exposure due to the
potential formation of hazardous photo-degradation products. Chemicals are more frequently tested for
photolysis under natural sunlight, leading to uncertainties in the extent and rate of indoor photolysis
reactions, particularly for chemicals contained in consumer articles and products.
In this protocol, a generic method is described to test the indoor photolysis potential of a chemical
contained within a consumer article or product. Test material is exposed to simulated sunlight, through
windows, in an accelerated weathering chamber. Potential photolysis products are detected from air (by
static air sampling), the surface of the test specimens (by wipe sampling), and settled dust (by dust
sampling).
7.3.2. Facility and Apparatus
7,3,2,1, Test Chamber
Photolysis tests are conducted in an accelerated weathering chamber, which includes an ultraviolet (UV)
irradiation source and temperature and humidity controls. Two types of weathering chambers are
commercially available (ASTM G154 and ASTM G155). Those that conform to ASTM G155 are
recommended for this protocol.
To simulate indoor lighting conditions, the system should have optical filters that generate sunlight
through window glass. This protocol has been developed for chamber systems conforming to ASTM D
4459-06 (Standard Practice for Xenon-Arc Exposure of Plastics Intended for Indoor Applications), which
provides spectral irradiance of approximately 0.3 (W/m2/nm) at 340 nm when operated in the
continuous light-on mode without water spray. This light source satisfies the light intensity requirement
of 5 W/m2 over the test specimens. For testing settled dust, the chamber model should allow the panels
to be placed on a horizontal (or nearly horizontal) tray.
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Note that the standard methods for accelerated aging tests under UV irradiation are intended to
measure changes in physical properties. To detect photolysis products, this test procedure requires
several modifications and additional steps, as described below.
7.3,2.2. Passive Air Sampler
Passive air samplers may be used to capture chemical vapors emitted from test specimens during
accelerated weathering. This method determines time-averaged concentrations by using polyurethane
foam (PUF) disks as the sampling media (Harrad & Abdallah, 2008). The PUF sampler is mounted onto
the chamber wall prior to a weathering test. The PUF sampler is removed from the chamber upon test
completion, is chemically extracted with solvents, and analyzed for potential photolysis products. The
analytical procedure should be optimized to the properties of the target chemicals.
733. Test Specimens
The product or article to be tested is cut into panels. Panel size may differ depending on the selected
chamber, but panel length and width should be uniform across all products or articles for a given
chamber. In general, it is recommended that panels for wipe sampling be at least 100 cm2 in size and
those for testing settled dust at least 500 cm2. For a given product or article, 12 panels are needed for
wipe sampling and 12 panels for testing settled dust.
73.4. Wipe Sampling
Wipe samples are collected to determine if photolysis products are present on the exposed surface of
the test specimens.
7.3.4.1. Wipe Sampling on Solid Surfaces
ASTM D 6661-10, Standard Practice for Field Collection of Organic Compounds from Surfaces Using Wipe
Sampling, or an equivalent method, is recommended for surface sampling on solid panels. The wipe
samples are subsequently extracted and analyzed for potential photolysis products.
7.3.4.2. Surface Sampling on Fabric Swatches
This method is based on the California roller method (Ross et al., 1991; Fuller et al., 2001) with
modifications. Use 3 in. by 6 in. heavy filter paper, instead of cotton gauze pads; place the fabric swatch
on a pre-cleaned, non-porous, flat surface (such as a rigid metal plate or polished granite block); place
the heptane-wetted filter paper on the fabric swatch; place a 3 in. by 6 in. stainless steel (or aluminum)
plate on the paper filter; add additional weights on the plate such that the total weight is 2 pounds (lb);
wait for 5 minutes; remove plate and weights; remove and extract the paper filter.
73.5. Dust Sampling
Photolysis may be difficult to detect on product or article surfaces by wipe sampling, and tests with
settled dust are recommended. Dust sampling should be conducted according to Protocol 6 (Transfer of
Chemicals from Source to Settled Dust) if there is a potential for chemical transfer to dust.
7.3.5.1. House Dust or Surrogate Dust
National Institute of Standards and Technology (NIST) house dust standard reference material SRM 2585
(NIST house dust), free of the chemical of interest, is recommended for this test method. The standard
house dust should be extracted and analyzed for chemical of interest background concentration prior to
product testing.
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The key properties of the dust to be reported include: dust density, organic carbon (OC) content, and
aerodynamic particle size distribution (e.g., geometric mean and geometric standard, 10-nm mean
diameter is recommended).
7.3,5.2. Dust Application
Test specimens are cut into panels at least 6 in. by 6 in. (15 cm by 15 cm), for tests with settled dust.
Test panels, besides fabrics, should be at least 5 mm thick. Apply an adequate amount of dust on the
test panels to achieve a target dust loading between 3.0 to 4.3 mg/cm2, which is roughly equivalent to
0.7 to 0.9 g dust per panel (See Protocol 6 for dust loading protocol).
7.3.6. Dust Collection from Test Panels
The procedure to collect dust samples from test panels is described in Protocol 6
7.3.7. Analytical Methods
Selection of the analytical methods for air, wipe, and dust samples depends on the properties of the
chemicals of interest and the type of sampling media. For example, for photolysis of decaBDE,
chromatography or mass spectrometry in electron capture negative ionization mode (GC/MS-ECNI) has
been used (Stapleton et al., 2008). Identification and quantification of photolysis products in the
samples are sometimes challenging because of the dominance of the chemical of interest (i.e., the
parent compound) in the chromatograms. This issue can be resolved by using a highly sensitive
instrument and by adopting a pre-separation method, such as preparative chromatography.
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7.3.8.
Dust
a.
b.
control
day 15
day 30
PUF disks
d.
f.
g-
h.
i.
Procedure for Photolysis Article Test without
Prepare 12 article panels measuring 3 in. by 6 in.
(7.6 cm x 15.2 cm)
Collect wipe samples from 3 control article
panels prior to aging and UV irradiation, to
represent initial surface conditions of the test
panels. Dispose of these three panels. Store wipe
samples, wrapped in foil, at 4ฐC until ready for
extraction and analytical quantification.
Clean the interior surfaces of the test chamber,
and sample tray by washing with soap and
water, wiping with toluene, and wiping with
methanol.
Collect two wipe samples, each covering 100 cm2
of the chamber walls. Store wrapped in
aluminum foil, at 4ฐC until ready for extraction
and analytical quantification but before the
expiration date.
Place three passive air samplers (PUF disks) on
the supporting cradle at half chamber height.
Sample height adjustments may be needed,
depending on the chemical of interest (consider
vapor density).
Place the remaining 9 panels on the sample tray.
Close the chamber door, set the temperature at
35 ฐC and relative humidity at 30% (The moisture
content is roughly equivalent to that of 50% RH
at 25 ฐC).
Turn on the UV light to start the test.
On day 4, turn off the UV light, open the chamber door, and perform the following steps:
o Remove three panels from the chamber and collect panel wipe samples,
o Remove one PUF disk for determination of time-integrated air concentrations of the
target chemical and potential photolysis products.
Close the chamber door and turn on the UV light to restart the test.
On day 15 and day 30, repeat the steps given for day 4.
After all panels have been removed, collect two wipe samples, each covering 100 cm2 of the
chamber walls.
1
temp: 35ฐC
RH: 30%
UV light
Figure 24. Graphic example of generic
procedure for photolysis without dust.
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7.3.9.
a.
b.
d.
h.
J-
k.
I.
m.
n.
control
day 4
m
-dust sample (x3)
day 15 day 30
PUF disks
ram
Procedure for Photolysis Article Test with Dust
Prepare 12 article panels measuring 6 in. by 6 in.
(15,2 cm x 15.2 cm)
Collect wipe samples from 3 article panels prior
to aging and UV irradiation, to represent initial
(control) conditions. Store wipe samples,
wrapped in foil, at 4ฐC until ready for extraction
and analytical quantification
Clean the interior surfaces of the test chamber,
and sample tray by washing with soap and
water, wiping with toluene, and wiping with
methanol.
Collect two wipe samples, each covering 100 cm2
of the chamber walls. Store wrapped in
aluminum foil, at 4ฐC until ready for extraction
and analytical quantification.
Place three passive air samplers (PUF disks) on
the supporting cradle at half chamber height.
Sample height adjustments may be needed,
depending on the chemical of interest (consider
vapor density).
Apply test dust onto panels according to the
method described in Protocol (6) Section 6.2.3.1.
Place the remaining 9 dust-loaded panels on the
sample tray.
Close the chamber door, set the temperature at
55 ฐC.
Do not use water spray for humidity control
because water droplets falling onto dust-loaded
test specimens may complicate the
interpretation of test results.
Turn on the UV light to start the test.
On day 4, turn off the UV light, open the chamber door, and perform the following steps:
o Remove three panels from the chamber.
o Remove one PUF disk for determination of time-integrated air concentrations of the
target chemical and potential photolysis products.
Close the chamber door and turn on the UV light to restart the test.
On day 15 and day 30, repeat the steps on day 4.
After all panels have been removed, collect two wipe samples, each covering 100 cm2 of the
chamber walls.
1
temp: 55ฐC
RM: NONE
UV light
Figure 25. Graphic example of generic
procedure for photolysis with dust.
7.3.10. General Procedure for Tests without UV-light
If the test results from Sections 7.3.8 and 7.3.9 suggest the presence of photolysis products in air,
surface or dust samples, it is recommended to conduct a test without the UV-light (i.e., dark cycle). This
is done by following the steps in Sections 7.3.8 and 7.3.9 with the UV light switched off.
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7.4. Records Retention and Reporting Results:
7.4.1. Records to be Maintained
Records submitted to the EPA should include, but are not limited to, the following:
a. The original signed protocol and any amendments.
b. Identification and characterization of the test substance as provided by Sponsor.
c. Identification and characterization of the material in question
d. Experiment initiation and termination dates.
e. Laboratory log books (e.g., stock solution concentration calculations and solution
preparation, calibration, and QC data).
f. Instrument (e.g., GC/ECNI) data files.
g. Spreadsheet files for data processing.
h. Environmental data acquired by the data acquisition system of the test chambers (e.g.,
temperature, air flow and inlet air moisture content).
i. Chain of custody documentation, including sample storage and handling information,
j. Copy of final report.
7.4.2. Final Report
A final report should be prepared, and records should be retained in accordance with 40 CFR 792,
Subpart J - Records and Reports.
The standard test methods mentioned above contain sections for reporting. For example, key
information to be reported includes:
a. Test material: material name, intended use, uniformity (homogeneous, layered, spray
application, coating, etc.), dimensions of test specimens, exposed area, treatment of sample
edges (sealed or exposed) and information about sample creation, transport, and storage (See
Contextualizing Information for Product Use).
b. Target chemical(s) and their basic properties: CAS number, molecular formula, vapor pressure,
chemical reactivity, concentration in material, etc. (See Contextualizing Information for Product
Use).
c. Test chamber: chamber type, model name, volume, dimensions, and interior surface material.
d. Test procedure: description or citation, including deviation from standard procedure.
e. Sampling methods for air, wipe, and dust samples and analytical methods description or
citation, including deviation from standard procedure. Description of accuracy and precision
f. Analytical methods: description or citation, including deviation from standard procedure.
g. Environmental conditions: lighting conditions (lamps, optical filter, light spectrum and intensity),
chamber temperature (expressed in arithmetic mean and standard deviation), and moisture
content in cooling air.
h. Test results: chromatograms of air, wipe and dust samples, identification of peaks, time-
averaged concentrations in chamber air from static air sampler, concentrations in wipe and dust
samples.
i. QA/QC data: accuracy and precision of measurements, calibrations, daily calibration checks,
background samples, blank samples.
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7.5. References:
Ashley, K., Applegate, G.T., Wise, T.J., Fernback, J.E., and Goldcamp, M.J. (2007). Evaluation of a
Standardized micro-vacuum Sampling method for Collection of Surface Dust. Journal of
Occupational and Environnemental Hygiene. 4: 215-223.
ASTM (2010). D6661-10 Standard Practice for Field Collection of Organic Compounds from Surfaces
Using Wipe Sampling. http://www.astm.org/Standards/D6661.htm
ASTM (2012). D4459-12 Standard Practice for Xenon-Arc Exposure of Plastics Intended for Indoor
Applications. http://www.astm.org/Standards/D4459.htm
ASTM (2012). G154-12a Standard Practice for Operating Fluorescent Ultraviolet (UV) Lamp Apparatus
for Exposure of Nonmetallic Materials http://www.astm.org/search/fullsite-
search.html?query=gl54&
ASTM (2013). G155-13 Standard Practice for Operating Xenon Arc Light Apparatus for Exposure of
Non-Metallic Materials, http://www.astm.org/search/fullsite-search.html?query=gl55&
Fuller, R., Klonne, D., Rosenheck, L., Eberhart, D., Worgan, J., and Ross, J. (2001). Modified California
Roller for Measuring Transferable Residues on Treated Turfgrass, Bulletin of Environmental
Contamination and Toxicology, 67: 787-794.
Harrad, S. and Abdallah, M.A. (2008). Calibration of Two Passive Air Sampler Configurations for
Monitoring Concentrations of Hexabromocyclododecanes in Indoor Air. Journal of Environmental
Monitoring, 10(4): 527-31.
Ross, J., Fong, H., Thongsinthusak, T., Margetich, S., and Krieger, R. (1991). Measuring Potential Dermal
Transfer of Surface Pesticide Residue Generated from Indoor Fogger Use: Using the CDFA Roller
Method Interim Report II. Chemosphere, 22: 975-984.
Stapleton, H.M. and Dodder, N.G. (2008). Photodegradation of Decabromodiphenyl Ether in House Dust
by Natural Sunlight. Environmental Toxicology and Chemistry, 27: 306-312.
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8. Migration to Saliva {Oral Exposure)
8.1. Purpose:
The objective of this protocol is to characterize chemical migration from an article or material into
simulated saliva overtime.
8.2. Modifications:
This protocol is general, and it is anticipated that during protocol development and finalization,
additional modifications will be made to tailor the sampling parameters or analytical techniques to the
specific chemical and product tested, as well as to Agency recommendations specific to particular
products, chemicals, or exposure scenarios of interest.
8.3. Description:
8.3.1. Approach
The methods for measuring migration from articles into simulated saliva have been described by the
European Commission Joint Research Centre (JRC) (Simoneau et al., 2001). The method was developed
and validated to estimate phthalate exposure from mouthing of soft plastic articles by children. The
method was validated by comparing the results with in vivo results from panels of adult volunteers who
mouthed articles or samples and collected their saliva. Several other studies have also used this
approach to estimate migration rates of chemicals into saliva (Bouma and Schakel 2001) (Bouma et al
2002) (Corea-Tellez et al 2008) (Earls et al 2003) (Masuck et al 2011) (Niino et al 2001) (Niino et al 2002)
(Niino et al 2003) (Ozer and Gucer 2011) (Simoneau et al 2009) (TNO Nutrition and Food Research 2001)
(lonas et al 2016). The U.S. Consumer Product Safety Commission (CPSC) recently characterized
exposure of phthalates, including mouthing, using migration rates measured using the head over heels
(HOH) approach (Babich, 2002) (Chen, 2002) (Babich etal., 2004). The method has also been applied to
characterize migration of flame retardants (Ghanem, 2015a) (Ghanem, 2015b). The HOH approach, also
referred to as aggressive agitation, measures the amount of chemical that migrates from an article into
simulated saliva. This migration is typically reported in ju.g/10 cm2/hour. Migration rates quantify the
rate at which a chemical that is a part of the article itself migrates from an article over time. Additional
information that characterizes the duration of the experiment and expected conditions of use, such as
duration of mouthing time for the article or material, is also needed to estimate exposure.
An alternate approach that quantified ingestion of dust settled on an article or the floor measures
transfer efficiency. "Hand to mouth" and "object to mouth" transfer efficiencies vary based on a
number of factors. A recently published transfer efficiency database contains all publicly available
transfer efficiency values and includes a discussion of methods for measuring oral saliva transfer
efficiency . (Gorman NG et al. 2012). However, the migration rate of chemicals that are components of
articles into saliva rather than the transfer of chemicals from the surface of an article to saliva is the
focus of this protocol. However, transfer efficiency measurements could also be used to inform
exposure estimates.
8.3.2. Preparation of Saliva
There are various approaches to prepare artificial saliva. It is recommended that saliva is prepared at a
representative temperature and pH and contain relevant enzymes and salts in concentrations likely to
be present within the human mouth. The composition of the saliva as well as the testing conditions of
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the saliva within the HOH testing apparatus should be transparent and well documented. An in vitro
model was developed to estimate extraction via saliva (Brandon et al 2006). That paper references a
composition of saliva from Versantvoort et al (2005), which is presented below. Another recent paper
(Marques et al 2011), provides five different approaches to simulate saliva, lonas et al 2016 is the most
recent paper to present an approach to developing simulated saliva.
8.3.2.1. Versantvoort et al 2005
a. Inorganic Solution: 10 mL of 89.6 g/L KCI solution,
10 mL of 20 g/L KSCN solution,
10 mL of 88.8 g/L NaH2P04 solution,
1.7 mL of 175.3 g/L NaCI solution, and
20 mL of 84.7 g/L NaHC03
Organic Solution: 8 mL of 25 g/L urea solution
Mix Inorganic and Organic Solutions:290 mg alpha-amylase,
15 mg uric acid, and
25 mg mucin
Adjust pH to pH 6.8 +/- 0.2
b.
c.
d.
8,3,2,2, Marques et al 2011
a. Simulated Saliva 1: 0.72 g/L KCI,
b. Simulated Saliva 2:
c. Simulated Saliva 3:
d. Simulated Saliva 4:
0.22 g/L calcium chloride dihydrate,
0.6 g/L NaCI,
0.68 g/L potassium phosphate monobasic,
0.866 g/L sodium phosphate dibasic (dodecahydrate),
1.5 g/L potassium bicarbonate,
0.06 g/L potassium thiocyanate, and
0.03 g/L citric acid with pH 6.5
0.72 g/L KCI,
0.22 g/L calcium chloride dihydrate,
0.6 g/L NaCI,
0.68 g/L potassium phosphate monobasic,
0.866 g/L sodium phosphate dibasic (dodecahydrate),
1.5 g/L potassium bicarbonate,
0.06 g/L potassium thiocyanate, and
0.03 g/L citric acid with pH 7.4
0.228 g/L calcium chloride dihydrate,
1.017 g/L NaCI,
0.204 g/L sodium phosphate dibasic (heptahydrate),
0.061 g/L magnesium chloride hexahydrate,
0.603 g/L potassium carbonate hemihydrate,
0.273 g/L sodium phosphate monobasic monohydrate,
1 g/L submaxillary mucin, and
2 g/L alpha-amylase
0.149 g/L KCI,
0.117 g/L NaCI,
2.1 g/L sodium bicarbonate,
2 g/L alpha-amylase, and
1 g/L mucin gastric
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e. Simulated Saliva 5: 8.0 g/L NaCI,
0.19 g/L potassium phosphate monobasic, and
2.38 g/L sodium phosphate dibasic (pH 6.8)
8.3.2,3, lonas et al 2016
a. Simulated Saliva: 4.5 g/L NaCI,
0.3 g/L KCI,
0.3 g/L Na2S04,
0.4 g/L NH4CI,
0.2 g/L urea, and
3.0 g/L lactic acid with pH 6.8
8.3.3. Preparation of Samples, Extraction, and Analysis
To prepare samples, discs, coupons, or circular samples are cut from the surface of the test article. The
diameter of the samples should be approximately 2 inches.
Note, for each extraction, 50 mL of simulated saliva is typically used. The weight and the volume of the
simulated saliva should be reported. Many test procedures and ASTM F963 require a 50:1 ratio of
solvent to sample for this type of extraction. Two extraction approaches are available. The ASTM F963
method requires that the samples be extracted four times each in 50 mL of simulated saliva in a 250 mL
Schott Duran (or similar) bottle for 30 minutes. Rotate the bottle head over heels (HOH) at 60 rpms for
the duration of the experiment at a vertical diameter of 2 feet (Figure 26).
The liquid simulated saliva extract is removed after each extraction and saved for analysis. A fresh 25 mL
of simulated saliva is added to the bottle containing the sample, and the bottle is shaken as above for 30
minutes. The replicate simulated saliva extract is then removed and also saved for analysis. The HOH
procedure is then repeated a third time. Each separate solution obtained from these shakings is
analyzed for the chemical of interest.
The second methodology, put forth in lonas et al 2016, requires that the sample and artificial saliva be
added to the specimen tube that is subsequently capped and placed on an incubating orbital shaker for
60 minutes at a rotation speed of 250 rpm and temperature of 37ฐC (Niino et al.. 2002).
~60 rpm
2 feet 30 minutes
| x4
50 mL simulated saliva
Figure 96. Graphic example of procedure for analyzing migration from product or article surface to saliva.
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For chemical analysis, 10 mL of the simulated saliva is placed in a test tube. One mL of xylene (or
suitable solvent, such as a 50:50 mix of dichloromethane and hexane) is added to the test tube and the
tube is sonicated for one minute. If concentration of the sample is required, the sample volume can be
reduced under nitrogen. Analyze the supernatant solvent for chemical content by a suitable
quantification method. A variety of analytical methods can be used depending on the chemical(s)
present. For example, GC/MS, inductively coupled plasma atomic emission spectroscopy (ICP) or HPLC.
Record the instrumentation conditions for whichever analytical technique is used. Combine the results
for the threeextractions, if using the HOH method.
8.4. Calculation of Migration Rate
The migration rate is a measure of the mass of chemical transferred from the article to the saliva,
normalized by the surface area of the article in contact with the saliva and the time of contact, as shown
in Equation 8-1.
, Mass ,
MR = 8-1
SAxTime
Where:
MR = Migration rate of chemical into saliva in mg/cm2/hr
Mass = Mass of chemical measured in the saliva sample, mg
S/4 = Surface area of article in contact with the saliva, typically 10 cm2
Time = Contact time between article and saliva, 1 hr
8.5. Records Retention and Reporting Results:
A final report should be prepared, and records should be retained in accordance with 40 CFR 792,
Subpart J - Records and Reports.
8.5.1. Records to be Maintained
Records submitted to the EPA should include, but are not limited to, the following:
a. The original signed protocol and any amendments.
b. Identification and characterization of the test substance as provided by Sponsor.
c. Identification and characterization of the material in question
d. Experiment initiation and termination dates.
e. Laboratory log books (e.g., stock solution concentration calculations and solution preparation,
calibration, and QC data).
f. Instrument (e.g., GC/ECNI) data files.
g. Spreadsheet files for data processing.
h. Chain of custody documentation, including sample storage and handling information.
i. Copy of final report.
8.5.2. Final Report
A final report should be prepared, and records should be retained in accordance with 40 CFR 792,
Subpart J - Records and Reports. For example, the following key information should be included in the
report:
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a. Test material: material name, intended use, uniformity (homogeneous, layered, spray
application, coating, etc.), and dimensions of test specimens. If the two sides of the material are
different, indicate which side is tested (See Contextualizing Information for Product Use).
b. Extraction solution: preparation, chemical makeup, testing
c. Test procedure: description or citation, including deviation from standard procedure.
d. Analytical methods: description or citation, including deviation from standard procedure.
e. Test results: mass migrated and concentrated in extraction solution.
f. Calculated results: migration rate.
g. QA/QC data: accuracy and precision of measurements, calibrations, daily calibration checks,
background samples, blank samples.
8.6. References:
Chen, S-B. (2002) Screening of toys for PVC and phthalates migration. June 20, 2002. In: CPSC:
Response to Petition HP 99-1. Request to ban PVC in toys and other products intended for children
five years of age and younger. U.S. Consumer Product Safety Commission, Bethesda, MD. August
13, 2002. See TAB I, pp. 244-261. https://www.cpsc.gov/s3fs-public/pdfs/foia fivevearpt4.pdf
Babich, M.A. (2002) Updated risk assessment of oral exposure to diisononyl phthalate (DINP) in
children's products. August 26, 2006. In: CPSC: Response to Petition HP 99-1. Request to ban PVC
in toys and other products intended for children five years of age and younger. U.S. Consumer
Product Safety Commission, Bethesda, MD. August 13, 2002. See TAB L, pp. 299-419.
https://www.cpsc.gov/s3fs-public/pdfs/foia fivevearpt5.pdf, https://www.cpsc.gov/s3fs-
public/pdfs/foia fivevearpt6.pdf, and https://www.cpsc.gov/s3fs-public/pdfs/foia fivevearpt7.pdf.
Babich MA, Greene MA, Chen S, Porter WK, Kiss CT, Smith TP, Wind ML (2004) Risk assessment of oral
exposure to diisononyl phthalate from children's products. Regulatory Toxicology and
Pharmacology 40: 151-167.
Bouma K and Schakel D.J., 2001. Plasticisers in Soft PVC Toys. Report number: NDTQY002/01. available
at https://www.nvwa.nl/txmpub/files/7p file id=10485
Bouma, K., & Schakel, D. J. (2002). Migration of phthalates from PVC toys into saliva simulant by
dynamic extraction. Food Additives & Contaminants, 19(6), 602 -610., available at
http://www.tandfonline.eom/doi/abs/10.1080/02652030210125137#.VgqkTJe2a8R
Brandon, E. F., Oomen, A. G., Rompelberg, C. J., Versantvoort, C. H., van Engelen, J. G., & Sips, A. J.
(2006). Consumer product in vitro digestion model: Bioaccessibility of contaminants and its
application in risk assessment. Regulatory Toxicology and Pharmacology, 44(2), 161-171.
Corea-Tellez, K. S., Bustamante-Montes, P., Garcia-Fabila, M., Hernandez-Valero, M. A., & Vazquez-
Moreno, F. (2008). Estimated Risks of Water and Saliva Contamination by Phthalate Diffusion from
Plasticized Polyvinyl Chloride. Journal of Environmental Health, 71(3), 34-9.. available at
http://europepmc.org/abstract/med/18990931
Earls, A. O., Axford, I. P., & Braybrook, J. H. (2003). Gas chromatography-mass spectrometry
determination of the migration of phthalate plasticisers from polyvinyl chloride toys and childcare
articles. Journal of chromatography A, 983(1). 237-246., available at
http://www.sciencedirect.com/science/article/pii/S0021967302Q17363
Ghanem, R. A. (2015a). Kinetics of thermal and photo-initiated release of tris (l,3-dichloro-2-propyl)
phosphate (TDCP) flame retardant from polyurethane foam materials. Journal of Environmental
Science and Health, Part A: Toxic/Hazardous Substances and Environmental Engineering, 50(8), 855-
865.
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Ghanem, R. A. (2015b). Kinetics of thermal and photo-initiated release of tris(l-chloro-2-propyl)
phosphate (TCPP) from polyurethane foam materials. Jordan Journal of Chemistry, 10(1), 20-33.
lonas, AC; Ulevicus, J; Gomez, AB; Brandsma, SH; Leonards, PEG; van de Bor, M; Covaci, A. (2016).
Children's exposure to polybrominated diphenyl ethers (PBDEs) through mouthing toys.
Environment International. 87:101-107.
http://www.sciencedirect.com/science/article/pii/S0160412015301Q21.
Masuck, I., Hutzler, C., & Luch, A. (2011). Estimation of dermal and oral exposure of Children to scented
toys: Analysis of the migration of fragrance allergens by dynamic headspace GC-MS. Journal of
separation science, 34(19), 2686-2696., available at
http://onlinelibrarv.wilev.com/doi/10.1002/issc.201100360/abstract;isessionid=CD01BF2ED5C27F0
3C6AClE405B78E4D6.f03t04?deniedAccessCustomisedMessage=&userlsAuthenticated=false
Marques, M. R., Loebenberg, R., & Almukainzi, M. (2011). Simulated biological fluids with possible
application in dissolution testing. Dissolution Technol, 18(3), 15-28 (Table 10).
Ng, M. G., Semple, S., Cherrie, J. W., Christopher, Y., Northage, C., Tielemans, E., Veroughstraete, V., &
Van Tongeren, M. (2012). The relationship between inadvertent ingestion and dermal exposure
pathways: A new integrated conceptual model and a database of dermal and oral transfer
efficiencies. Annals of Occupational Hygiene. 56(9): 1000-1012.
Niino T, Ishibashi T, Itho T, Sakai S, Ishiwata H, Yamada T, and Onodera S, 2001. Monoester formation
by hydrolysis of dialkyl phthalate migrating from PVC products in human saliva. Journal of Health
Science, 47(3):318-322., available at http://ihs.pharm.or.jp/data/47%283%29/47%283%29p318.pdf
Niino T, Ishibashi T, Itho T, Sakai S, Ishiwata H, Yamada T, Onodera S, 2002. Comparison of Diisonoyl
Phthalate Migration from Polyvinyl chloride products into human saliva in Vivo and into saliva
simulant In vitro. Journal of Health Science, 48(3):227-281., available at
http://ihs.pharm.or.jp/data/48%283%29/48 277.pdf?origin=publication detail
Niino T, Asakura T, Ishibashi T, Itho T, Sakai S, Ishiwata H, Yamada T, Onodera S, 2003. A Simple and
Reproducible Testing Method for Dialkyl Phthalate Migration from Polyvinyl Chloride Products into
Saliva Simulant. J. Food Hyg. Soc. Japan 44, 1: (13-18), available at
https://www.istage.ist.go.jP/article/shokueishi/44/l/44 1 13/ pdf
Ozer, E. T., & Giiger, ง. (2011). Determination of some phthalate acid esters in artificial saliva by gas
chromatography-mass spectrometry after activated carbon enrichment. Talanta, 84(2), 362 -367.,
available at http://www.sciencedirect.com/science/article/pii/S00399140110Q035X
Simoneau, C., Hannaert, P., and Sarigiannis, D. E. 2009. Effect of the nature and concentration of
phthalates on their migration from PVC materials under dynamic simulated conditions of mouthing.
EUR 23813 EN: pp. 20.,available at
http://publications.irc.ec.europa.eu/repositorv/bitstream/JRC51604/reqno irc51604 chemtest par
t2-phthalates release toys cs02009 05 26.pdf%5Bl%5D.pdf
TNO Nutrition and Food Research, 2001. Migration of phthalate plasticizers from soft PVC toys and
childcare articles -Final report. Netherlands Organization for Applied Scientific Research, available
at http://ec.europa.eu/enterprise/sectors/chemicals/files/studies/phthalates2 en.pdf
Versantvoort, C. H., Oomen, A. G., Van de Kamp, E., Rompelberg, C. J., & Sips, A. J. (2005). Applicability
of an in vitro digestion model in assessing the bioaccessibility of mycotoxins from food. Food and
Chemical Toxicology, 43(1), 31-40.
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9. Migration to Skin {Derma! Exposure!
9.1. Purpose:
The objective of this protocol is to determine chemical loading on the surface of the skin due to direct
contact with an article or product (solid or liquid), contact with chemical laden dust or soil, and vapor-to
skin exposure, and to quantify potential availability for dermal exposure.
9.2. Modifications:
This protocol is general, and it is anticipated that during protocol development and finalization,
additional modifications will be made to tailor the sampling parameters or analytical techniques to the
specific chemical and product tested, as well as to Agency recommendations specific to particular
products, chemicals, or exposure scenarios of interest.
9.3. Description:
For this protocol, actual skin (i.e. animal skin, cadaver skin, human subject skin, where proper ethical
and scientific research requirements have been met, etc.) or a skin surrogate, such as filter paper, may
be used to estimate chemical load present on the surface of the skin. If human subjects are used for the
testing, ensure that all requirements related to issues associated with scientific and ethical aspects of
human subject research are followed. There are four primary mechanisms for chemical loading on to the
surface of the skin:
a. Contact through application of liquid or semi-solid products or products
b. Contact with surface of article or building material and migration into simulated sweat and/or
skin lipids (oil).
c. Contact with dust and or soil and migration into simulated sweat and/or skin lipids (oil).
d. Transfer of chemicals from vapor-phase chemical concentrations in the air to the skin.
The first mechanism applies primarily to products; the second to articles; the third to dust and soil which
may be present on the surface of articles, on the floor, or the ground. The fourth mechanism can occur
as a result of product use or article exposure if individuals are exposed to elevated air concentrations for
a long enough duration for transfer to occur. This exposure pathway may also be significant depending
on the chemical, product, and environment of interest for the exposure scenario. Methods, such as
those presented by Weschler et al, 2015 and Gong et al, 2014, show promise, and information from
studies like this could inform an expanded basis for protocols characterizing the dermal pathway in the
future.
Note, potential dermal exposure is described here. There are approaches available to estimate
absorbed dose if dermal exposure is expected to be an important exposure pathway but this is outside
the scope of this protocol. In vivo measurements, in vitro measurements and/or measured permeability
coefficients could be used to estimate absorbed dose. The flux of a chemical across the skin membrane,
whether an infinite or finite dose is assumed, exposure duration, and comparison of different
approaches can be considered (OECD 2004a) (OECD 2004b) (Buist et al 2010) (Frasch et al 2014).
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9.3.1. Approach for Determination of Skin Loading through Direct Wipe sampling or measurement of
Film Thickness from Application of Liquids or Semi-solid Product
Direct contact exposure from products may result from either direct application to skin, or via direct
contact with a product not intentionally applied to the skin. The thickness of the product film that
remains on the skin after contact is used to characterize the mass of product on the skin. The film
thickness can be measured in up to five use scenarios depending on the intended product use. In all
scenarios, the product should be prepared according to use instructions. Because the test is measuring
product film thickness on skin as a result of product use, a surrogate test product with similar properties
(e.g., volatility, viscosity, etc.) can be used for testing. For example, surrogate test products that are
generally regarded as safe and non-toxic should be used if human subjects will be used during testing.
Product specific density should be measured and used alongside film thickness measurements to
estimate skin loading (mg/cm2).
Skin Wipes and/or manual handwashing can also be used to sample the skin directly. These sampling
strategies have been employed for several decades in occupational settings, but are also relevant to
indoor exposures associated with products and articles. Chemical substances present on the skin are
extracted using these techniques and provide a snapshot of the mass available for exposure at the time
the samples were taken. Skin wipes are typically wetted with a combination of water and solvent. The
wipe should be applied with the same approach and the number of wipes, surface area of skin, sampling
efficiency, and time of sample following exposure should be noted. Hand washes are typically a
combination of water, soap, and solvent. The hand wash should be done consistency with the number
of washes, surface area of skin, sampling efficiency, and time of sample following exposure noted.
Interpretation of wipe samples, particularly for more volatile compounds should be carefully considered
as sampling efficiency is typically less than 100% and varies depending on how and when the sample
was collected (Brouwer et al 2000).
9.3.1.1. Primary and Secondary Contact
For the initial contact scenario, a cloth saturated with the product should be rubbed over the front and
back of both clean, dry hands. For the secondary contact scenario, a cloth saturated with the product
should be rubbed over the front and back of both hands for a second time, after as much as possible of
the liquid that adhered to skin during the first contact event was removed using a clean cloth. The
subject's hands should then be fully wiped, defined as wiping with a clean dry cloth as thoroughly as
possible for 10 seconds. The film thickness is determined by dividing the difference in cloth weight
before and after wiping by the surface area of the hand and the density of the prepared product. Four to
6 replicate tests should be conducted and reported.
9.3.1.2. Immersion
To measure the film thickness that results from immersion, the hand should be immersed in the
prepared product and then allowed to drip back into the container for 30 seconds. The weight of the
container of prepared product should be weighed before and after immersion. The difference in weight
of the container divided by the surface area of the hand, normalized by the density of the product is the
film thickness. Four to 6 replicate tests should be conducted and reported.
9.3.1.3. Contact from Handling a Wet Rag
To estimate film thickness from handling a wet rag, a cloth saturated with the product should be rubbed
over the palms of both hands in a manner simulating handling of a wet cloth. The subject's hands should
then be fully wiped, defined as wiping with a clean dry cloth as thoroughly as possible for 10 seconds.
The film thickness is determined by dividing the difference in cloth weight before and after wiping by
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the surface area of the hand and the density of the prepared product. Four to 6 replicate tests should be
conducted and reported.
9.3.1.4. Contact from Cleaning a Spill
A subject should use a clean cloth to wipe up 50 mL of prepared product poured onto a non-porous
surface. After cleanup, the subject's hands should then be fully wiped, defined as wiping with a clean dry
cloth as thoroughly as possible for 10 seconds. The film thickness is determined by dividing the
difference in cloth weight before and after wiping by the surface area of the hand and the density of the
prepared product. Four to 6 replicate tests should be conducted and reported.
93.2. Approach for Estimating Migration into Simulated Sweat from Contact with an Article
A small or large scale experiment can be used to evaluate sweat facilitated migration from an article
onto skin or skin surrogate. The sampling conditions should be varied based on the chemical, article,
and scenario of interest. Parameters that should be varied include the:
a. size and thickness of the article,
b. amount of surrogate sweat applied,
c. amount and timing of pressure (psi) applied,
d. size of skin or skin surrogate material used,
e. type of surrogate material used (if applicable), and
f. additional barrier present or not present between article surface and surrogate skin material of
filter paper.
9.3 .2.1. Preparation of Sweat and/or Simulated Sweat/Sebum Mixture (Skin Lipids)
Artificial sweat or perspiration is the reagent extract solution. Typical components of artificial sweat
include water, lactate, urea, sodium, potassium, calcium, and magnesium. Saline solution may be used
as a starting point. Because the swelling of water-soluble polymers is suppressed by some metal ions,
especially calcium, and by low pH, Marques et al. (2011) provide five different approaches to simulate
sweat with different concentrations of calcium and different pH.
a. Simulated Sweat 1 (3 milliequivalents of calcium ions): 2.92 mEq/L NaCI,
0.166 mEq/L CaCI2,
0.12 mEq/L MgS04, and
1.02 mEq/L potassium phosphate monobasic (pH 5.4)
b. Simulated Sweat 2 (60 milliequivalents of calcium ions):5.49 mEq/L NaCI,
3.32 mEq/L CaCI2,
0.24 mEq/L MgS04, and
1.36 mEq/L potassium phosphate monobasic (pH 4.5)
c. Simulated Sweat 3 (120 milliequivalents of calcium ions): 5.49 mEq/L NaCI,
6.64 mEq/L CaCI2,
0.24 mEq/L MgS04, and
1.36 mEq/L potassium phosphate monobasic (pH 4.5)
d. Simulated Sweat 4 (240 milliequivalents of calcium ions): 5.49 mEq/L NaCI,
13.28 mEq/L CaCI2, and
0.24 mEq/L MgS04, 1.36 mEq/L potassium
phosphate monobasic (pH 4.5)
e. Simulated Sweat 5: 0.5 % (in mass) NaCI,
0.1 % lactic acid, and
0.1 % urea with the recommended volume of simulated fluid
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(about 1 mL per cm2 sample area)
f. Simulated Sweat/Sebum Mixture 6 (pH 5.3) (Abdallah et al 2016):
Sodium Sulfate- 5.83 x 10-2 g/L
Copper Chloride anhydrous-1.60 x 10-4 g/L
Ammonium Hydroxide -1.82 x 10-1 g/L
Iron sulfate Heptahydrate - 2.72 x 10-3 g/L
Sulfur- 7.37 x 10-2- g/L
Lead- Reference Solution 1000 ppm - 2.49 x 10-5 g/L
Manganese- Reference Solution 1000 ppm -1.38 x 10-4 g/L
Nickel- Reference Solution 1000 ppm - 2.46 x 10-5 g/L
Zinc - Reference Solution 1000 ppm - 8.5 x 10-4 g/L
Sodium Bicarbonate - 2.52 x 10-1 - g/L
Potassium chloride - 4.55 x 10-1 -g/L
Magnesium Chloride Hexahydrate -1.67 x 10-2- g/L
Sodium Phosphate Anhydrous Monobasic - 4.84 x 10-2- g/L
Calcium Chloride Dihydrate- 7.65 x 10-1 - g/L
Sodium chloride- 5.84 xl0-2 - g/L
Acetic Acid 7.81 x 10-3- g/L
Butyric Acid- 2.11 x 10-4- g/L
D(+) -Glucose- 3.06 x 10-2- g/L
Lactic Acid-1.57 x 100- g/L
Essential Amino Acid Mix- 2.5 mM each : 17 AA g/L
Ammonium Chloride- 9.92 x 10-3- g/L
Urea-6.01x10-1-g/L
Creatinine - 9.50 x 10-3- g/L
Squalene- 0.5151- g/L
Palmityl Palmitate (saturated)- 0.9718- g/L
Triolein (Unsaturated)- 0.5345 g/L
Cholesteryl Oleate- 0.0972- g/L
9.3.3. Preparation of Samples, Extraction, and Analysis
A small-scale experiment can be used to evaluate an article coupon with surface area corresponding to a
circle with a diameter of 5.5 cm (Bhooshan and Cobb 2000), as demonstrated in Figure 27. The article
sample, potentially containing multiple layers of an article, such as fabric and foam, is placed in a 600 mL
beaker and covered with skin or skin surrogate, such as Whatman #2 filter paper, large enough to cover
the article sample.
Two to 4 mL of simulated sweat extract is poured onto the skin or skin surrogate. The skin or skin
surrogate and article surface are allowed to dry for 6-8 hours, and the skin or skin surrogate is removed.
The surface of the article in the beaker is then covered with another skin or skin surrogate and the
experiment is repeated with the same simulated sweat solution four times, for a total of 5 skin or skin
surrogate samples. It is recommended to consider the application of pressure to the skin or skin
surrogate covered article using a range of weights (i.e. one psi weight measuring 2 inches in diameter
and weighing 3.4 lbs, or other weights consistent with typical and high-end dermal contact) in a portion
of the replicates. If the article being tested contains a barrier material (i.e., textile covering of a couch
cushion), this should be considered in the testing; the replicates should consider migration both with
and without the presence of such a barrier between the skin or skin surrogate and the article. After
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collection and drying, the five skin or skin surrogate replicate samples are then extracted and analyzed
for the chemical of interest.
'5.5cm
optional psi weights
filter paper
2-4 mL simulated sweat
Figure 107. Graphic example of small-scale procedure for analyzing migration from product or article surface to
sweat.
As an alternative, a large scale experiment could be conducted to evaluate a larger surface area of an
article including up to full size (e.g., full couch cushion, pillow, and mattress) (Cobb 2005). The actual
surface area and thickness of the article used in the experiment may vary but should be documented.
Two skin or skin surrogate pieces should be placed on the entire surface of the article and wetted with
25 mL of simulated sweat. Note, the amount of simulated sweat may vary depending on the physical
activity level and age of an individual so a range of simulated sweat amounts can be considered.
One psi weight should be placed on each skin or skin surrogate piece. One weight should be removed
after the skin or skin surrogate is thoroughly wetted; the other should be removed six hours after
application of the simulated sweat. The first situation mimics intermittent skin contact with the article
while the second mimics continuous skin contact with the article. The surface of the article is then
covered with two new dry pieces of skin or skin surrogate and the experiment is repeated with the same
simulated sweat solution four times, for a total of 5 tests with 10 filter paper samples collected. Five
replicate tests are done for each sample. If the article being tested contains a barrier material (i.e.,
textile covering of a couch cushion), this should be considered in the testing; the replicates should
consider migration both with and without the presence of such a barrier between the skin or skin
surrogate and the article. The 10 skin surrogate samples are then extracted and analyzed for the
chemical of interest.
Barrier materials and/or the surfaces of the articles themselves may or may not be treated with various
chemicals, which are intended to promote stain resistance, water repellence, etc. The use of materials
with these chemicals added is applicable if representative of the exposure scenario of interest. If a
barrier material of any kind is used, the experiments should be repeated five times both with and
without the use of the barrier material.
These experiments can be described as surface migration tests that estimate the quantity of chemical
that might migrate to the skin from the surface of an article over time under certain conditions of use.
Extraction methods and analytical approaches for the skin or skin surrogate, such as filter paper, will
vary based on the chemical and exposure scenario of interest.
9.3.4. Approach for Estimating Migration into Simulated Sweat from Contact with an Article
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9.4. Records Retention and Reporting Results:
A final report should be prepared, and records should be retained in accordance with 40 CFR 792,
Subpart J - Records and Reports.
9.4.1. Records to be Maintained
Records submitted to the EPA should include, but are not limited to, the following:
a. The original signed protocol and any amendments.
b. Identification and characterization of the test substance as provided by Sponsor.
c. Identification and characterization of the material in question
d. Experiment initiation and termination dates.
e. Laboratory log books (e.g., stock solution concentration calculations and solution preparation,
calibration, and QC data).
f. Instrument (e.g., GC/ECNI) data files.
g. Spreadsheet files for data processing.
h. Environmental data acquired by the data acquisition system of the test chambers (e.g.,
temperature, air flow and inlet air moisture content).
i. Chain of custody documentation, including sample storage and handling information,
j. Copy of final report.
9.4.2. Final report
A final report should be prepared, and records should be retained in accordance with 40 CFR 792,
Subpart J - Records and Reports. For example, the following key information should be included in the
report:
a. Test material: material name, intended use, uniformity (homogeneous, layered, spray
application, coating, etc.), and dimensions of test specimens. If the two sides of the material are
different, indicate which side is tested (See Contextualizing Information for Product Use).
b. Target chemical(s) and their basic properties: CAS number, molecular formula, vapor pressure,
chemical reactivity, concentration in material, etc. (See Contextualizing Information for Product
Use).
c. Extraction solution: preparation, chemical makeup, testing.
d. Test procedure: description or citation, including deviation from standard procedure.
e. Analytical methods: description or citation.
f. Test results: mass migrated and concentrated in extraction solution.
Calculated results: migration rate
9.5. References:
Bhooshan, B., and Cobb, D. (2000). Migration of Flame Retardant Chemicals from Upholstery Fabrics.
TAB G. Pages 610-638.
Brouwer et al (2000). Hand Wash and Manual Skin Wipes. Ann. occup. Hyg., 44, (7):. 501-510.
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Cobb, D. (2005). Migration of Flame Retardant Chemicals in Mattress Barriers. H. Pages 542-553,
available at http://www.cpsc.gov/PageFiles/88231/matttabh.pdf
Buist, H. E., van Burgsteden, J. A., Freidig, A. P., Maas, W. J., & van de Sandt, J. J. (2010). New in Vitro
Dermal Absorption Database and the Prediction of Dermal Absorption under Finite Conditions for
Risk Assessment Purposes. Regulatory Toxicology and Pharmacology, 57(2): 200-209.
Frasch, H. F., Dotson, G. S., Bunge, A. L., Chen, C. P., Cherrie, J. W., Kasting, G. B., Kissel, J.C., Sahmel J.,
Semple S. and Wilkinson, S. (2014). Analysis of Finite Dose Dermal Absorption Data: Implications for
Dermal Exposure Assessment. Journal of Exposure Science and Environmental Epidemiology, 24(1):
65-73.
Gong, M., Zhang, Y., & Weschler, C.J. (2014). Measurement of Phthalates in Skin Wipes: Estimating
Exposure from Dermal Absorption. Environmental Science & Technology, 48: 7428-7435
Marques, M. R., Loebenberg, R., & Almukainzi, M. (2011). Simulated Biological Fluids with Possible
Application in Dissolution Testing. Dissolution Technol, 18(3): 15-28 (Table 17).
Organization for Economic Co-operation and Development, (2004a). (Test Guideline 428) Skin
Absorption-ln vitro Method.
Organization for Economic Co-operation and Development, (2004b). (Section 4-Other Test Guidelines)
Guidance Document for the Conduct of Skin Absorption Studies.
Pawar, G., Abdallah, M. A. E., de Saa, E. V., & Harrad, S. (2017). Dermal bioaccessibility of flame
retardants from indoor dust and the influence of topically applied cosmetics. Journal of Exposure
Science and Environmental Epidemiology, 27, 100-105.
Weschler, C.J., Beko, G., Koch, M., Salthammer, T., Schripp, T., Toftum, J. Claesen, G. (2015) Transdermal
Uptake of Diethyl Phthalate and Di(n-butyl) Phthalate Directly from Air: Experimental Verification.
Environmental Health Perspectives, 123: 928-934. http://dx.doi.org/10.1289/ehp.1409151.
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10.Migration of Chemical from Solid Material to Water
10.1. Purpose:
The objective of the leaching protocols is to determine the potential for migration of chemicals into
water, and the rate of release of chemicals from various solid materials into water. The protocol is
divided into two sections: the first section informs understanding of liquid to solid ratio and the
potential for migration; the second section informs an understanding of the longer-term migration
through derivation of a migration rate. The methods presented are not applicable to volatile
compounds, and generally suitable only for testing chemicals with a vapor pressure less than 0.1 torr
(~10 Pascal) at 25ฐC.
10.2. Modifications:
This protocol is general, and it is anticipated that during protocol development and finalization, Agency
recommendations will be incorporated to tailor sampling parameters or analytical techniques to the
specific product, chemical, and exposure scenario of interest.
10.2.1. Key Definitions
Extractant-the solution used to leach a chemical from the solid material. In this protocol the extractant
is water.
Leachate - the solution after testing which includes the extractant and leachables from the solid
material.
Leachables - chemical contained within the leachate.
Solid
material
'Extractant!
Chemical A
Leaching
vessel
^ Chemical B
Chemical C
Leachate
Leachables
Figure 28. Diagram of relationships between components in leaching protocol.
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Section 10a: Migration into Water: Liquid to Solid Ratio
scription:
Section 10a of the protocol is used to determine the liquid-solid partitioning (LSP) of inorganic chemicals
(including metals), non-volatile organic compounds (dissolved organic carbon), and semi-volatile organic
compounds (SVOCs) at environmentally relevant temperatures as a function of liquid-to-solid ratio (L/S)
under conditions close to liquid-solid chemical equilibrium. This method is a modification of EPA Method
1316.
10.3.1. Approach
This method consists of five parallel leaching experiments of ground or crumbled solid material in
reagent water over a range of L/S values from 0.5 to 10 mL extractant/g dry material. In addition to the
five leaching experiments, a method blank without a solid sample is carried through the procedure in
order to verify that analyte interferences are not introduced as a consequence of reagent impurities or
equipment contamination. In total, six bottles are tumbled in an end-over-end fashion for a specified
contact time based on the maximum particle size of the solid. At the end of the contact interval, the
liquid and solid phases are roughly separated via settling or centrifugation. Extract pH and specific
conductance of the liquid phase are then measured. The bulk of the leachate is clarified by pressure or
vacuum filtration in preparation for constituent analysis. Analytical aliquots of the extracts are collected
and preserved accordingly based on the determinative methods to be performed. The leachate
constituent concentrations are plotted as a function of L/S and compared to QC and assessment limits.
10.3.2. Materials and Equipment
Laboratory apparatus and supplies that will be necessary for the testing include:
ASTM type 2 water (ASTM, 2011) or other types of high purity laboratory water
0.01 M NaOH and 0.1 M HCL solution
Six wide-mouth bottles of inert material, including five for test samples and one for a method
blank. Bottles made of High Density Polypropylene (HDPP) are recommended for the evaluation
of organic and inorganic chemicals. The bottles should be leak-proof and be of sufficient volume
for to hold both the solid sample and extractant volume
Balance with readability of 0.01 gram
Rotary tumbler capable of rotating extraction vessels end-over-end at a constant speed of 28ฑ2
rpm
Filtration apparatus (pressure or vacuum filtration)
Filtration membranes with 0.45 urn pore size
pH meter
Conductivity meter
Oxidization-reduction potential (ORP) meter
Adjustable-volume pipettor
Disposable pipettor tips
Centrifuge (recommended) able to centrifuge extraction vessels at 4000ฑ100 rpm for 10ฑ2 min
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10.4. Experimental Design:
10.4.1. Sample Preparation Procedure
For this procedure, 85% (by weight) of particles should be less than 2.0 mm. Particle size reduction of
"as received" sample may be achieved through crushing, milling, or grinding, provided that all
equipment surfaces in contact with the test materials are chemically inert. During the reduction process,
care should be taken to minimize sample loss, including loss of volatile constituents in the sample. Once
particles are of relatively uniform size, sieve the sample and calculate the percentage (by weight) less
than the sieve size. Continue particle size reduction until at least 85% of particles pass through the sieve.
If the moisture content of the sample is estimated to be >10% then the actual moisture content should
be determined prior to testing (see Appendix 10A).
Samples should not have preservatives added prior to leaching. Samples may be refrigerated after
collection and prior to leaching, unless it will result in irreversible physical change to the sample.
Table 8 below is an example experimental schedule that can be used as a guide. Each volume of sample
material should be tested in duplicate.
Table 8. Example Experimental Schedule1'2.
A
B
C
D
E
F
Test
Target LS
Minimum Dry
Mass of "as
Volume of
Recommended
position
(mL extractant/g
Mass (g-dry)
tested"
reagent
bottle size (mL)
dry material)
sample (g)
water
(mL)
T01
10.0
10
11.1
99
150
T02
5.0
20
22.2
98
150
T03
2.0
50
55.5
94.5
250
T04
1.0
100
111.1
89
250
T05
0.5
200
222.2
78
500
B013
QC
-
-
100
150
TOTAL
422.1
558.5
1This schedule assumes a target liquid of lOOmL
2This schedule is based on "as tested" solids contents of 0.90 g-dry/g
3Test position marked B01 is a method blank of reagent water
The following calculation can be performed to set up a similar experimental table. Calculate and record
the volume of reagent water needed to bring each leaching experiment to the target L/S ratio in Column
F of Table 1 using Equation 10-1:
VRW = Mdry X LS [10-1]
Where:
VRW = volume of reagent water needed to complete L/S (mL)
Mdry = mass of dry material (g-dry)
LS = liquid-to-dry-solid ratio ( mL/g)
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The size of the leaching bottle should be sufficient to contain the combined volume of solid material and
extractant, ideally with a minimum amount of headspace. The mass of solids (Column D) in an extraction
may be scaled to minimize headspace in each leaching vessel. However, the volume of extractant should
always be based on the target L/S in Column B of Table 8.
10.4.2. General Leaching Test Procedure
This protocol uses a parallel batch procedure to determine the liquid-solid partitioning of a chemical
substance from a solid material. The general steps for this procedure are:
Adjust the reagent water to pH 7 with 0.01 M NaOH or 0.1 M HCL solution.
Measure the pH, specific conductivity, and ORP of the reagent water, and starting concentration
of chemical substance in the solid, prior to test.
Label bottles with test position numbers and method blank bottle according to the experimental
schedule.
Place the dry-mass equivalent of "as-tested" sample as shown in Column D in Table 8 into each
of the five test position leaching vessels.
Add the appropriate volume of reagent water to both the test position and method blank
leaching vessels as specified in Column F of Table 8.
Tighten the leak-proof lid on each bottle and tumble all leaching vessels (i.e., test vessels and
method blanks) in an end-over-end fashion at 28ฑ2 rpm at room temperature (20ฐC) for 48ฑ2
hours.
Remove the leaching vessels from the rotary tumbler and clarify the leachates by allowing the
bottles to stand or centrifuge the extraction vessels. If after settling or centrifugation, the
sample is not fully clarified, the sample may be filtered prior to leachate measurements (pH,
conductivity, and oxidization-reduction potential). If this is done, make a note of the deviation in
procedure records.
For each leaching vessel, decant a minimum volume of supernatant into a clean container.
Measure and record the pH, specific conductivity, and ORP of the leachates within 15 minutes of
leachate processing (see EPA Methods 9040, 9045, and 9050).
Separate the solid from the remaining liquid in each leaching vessel by pressure or vacuum
filtration through a clean 0.45-nm pore size membrane. The filtration apparatus may be
exchanged for a clean apparatus as often as necessary until all liquid has been filtered.
Immediately, preserve and store the volume(s) of leachate required for chemical analysis.
Preserve all analytical samples in a manner that is consistent with the determinative chemical
analyses to be performed (see section below).
Leachates may be preserved as appropriate based on individual determinative methods for
chemicals of concern.
10.4.3. Analytical Procedure
This protocol covers a wide range of chemical substances leaching from samples, which require different
analytical methods. Table 9 provides a list of EPA analytical methods for various chemicals.
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Table 9. EPA Analytical Methods for various chemicals.
Chemical
EPA Method
Lead
200.8 Methods for the Determination of Metals in
Environmental Samples, Supplement 1
Mercury
200.8 Methods for the Determination of Metals in
Environmental Samples, Supplement 1
245.1 Determination of Mercury in Water by Cold Vapor
Atomic Absorption Spectrometry
245.1 Methods for Chemical Analysis of Water and Wastes
Organic contaminants
List of EPA methods
PCBs
8082A Polvchlorinated Biphenvls (PCBs) by Gas
Chromatography
SVOCs
8270D Semi-volatile Organic Compounds by Gas
Chromatography/Mass Spectrometry (GC/MS)
10.5. Reporting of Results and Records Retention:
10.5.1. Records to be Maintained
Records submitted to the EPA should include, but are not limited to, the following:
a) The original signed protocol and any amendments.
b) Identification and characterization of the test substance as provided by Sponsor.
c) Identification and characterization of the material in question.
d) Batch ID of material used in characterization step and of material used in leaching step.
e) Experiment initiation and termination dates.
f) Laboratory log books (e.g., stock solution concentration calculations and solution
preparation, calibration, and QC data).
g) Instrument (e.g., GC/ECNI) data files.
h) Spreadsheet files for data processing.
i) Copy of final report.
10.5.2. Final Report
A final report of the results of the study should be prepared and submitted to the EPA. The final report
should include, but is not limited to the following, when applicable:
a. Name and address of facility performing the study.
b. Dates on which the study was initiated and completed.
c. Objectives and procedures stated in the approved protocol, including any changes in the
original protocol.
d. Identification and characterization of the test substance as provided by sponsor.
e. A summary and analysis of the data and a statement of the conclusions drawn from the
analysis.
f. A description of the transformations and calculations performed on the data.
g. A description of the methods used and reference to any standard method employed.
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h. A description of the instrumentation utilized.
i. A description of the preparation of the test solutions, the testing concentrations, and the
duration of the test.
j. A description of sampling and analytical methods, including level of detection, level of
quantification, and references,
k. A description of test specimens and test matrix.
I. A description of the test results including measured values for individual chemicals of
interest for each matrix,
m. A description of all circumstances that may affect the quality or integrity of the data,
n. The name of the study director, the names of other scientists or professionals, and the
names of all supervisory personnel involved in the study.
0. The signed and dated reports of each of the individual scientists or other professionals
involved in the study, if applicable.
p. The location where the raw data and final report are to be stored,
q. A statement prepared by the Quality Assurance Unit listing the types of instrumental
inspections, calibration certifications, the dates that the study inspections were made and
the findings reported to the Study Director and Management,
r. A copy of all raw data including but not limited to instrumentation output, lab notebooks,
and data sheets, etc.
Specific data that should be reported includes:
a. Date and time at the start of the test.
b. Name of the solid material.
c. Ambient temperature during migration.
d. Leaching contact time.
e. Concentration of chemical substances (leachables) in the starting material.
The minimum set of data that should be reported for each leachate includes:
a. Leachate sample ID.
b. Target L/S (mL/g-dry).
c. Mass of "as tested" solid material used (g).
d. Moisture content of material used (gH2o/g) (if moisture content of sample >10%).
e. Volume of extractant used (mL).
f. Measured final leachate pH.
g. Measured leachate conductivity (mS/cm).
h. Measured ORP (mV) (optional).
1. Concentrations of target leachables in leachate.
j. Analytical QC qualifiers as appropriate.
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10.53. Changes to the Final Report
If it is necessary to make corrections or additions to the final report after it has been accepted, such
changes should be made in the form of an amendment issued by the Study Director. The amendment
should clearly identify the part of the study that is being amended and the reasons for the alteration.
Amendments should be signed and dated by the Study Director and Laboratory Quality Assurance
Officer.
10.5.4. Changes to the Protocol
Planned changes to the protocol should be in the form of written amendments signed by the Study
Director and approved by the sponsor's representative and submitted to EPA using procedures in 40 CFR
790.50. Amendments should be considered as part of the protocol and should be attached to the final
protocol. Any other changes should be in the form of written deviations signed by the Study Director
and filed with the raw data. All changes to the protocol should be indicated in the final report. Changes
to the test standard require prior approval from EPA using procedures in 40 CFR 790.55.
10.6. References:
U.S. EPA. (2012) Method 1316. Liquid-solid partitioning as a function of liquid-to-solid ratio in solid
materials using a parallel batch procedure, https://www.epa.gov/sites/production/files/2015-
12/documents/1316.pdf
ASTM (2011). D1193 - 06(2011) Standard Specification for Reagent Water.
https://www.astm.org/Standards/D1193.htm
Section 10b: Migration Rate into Water over Time
scription:
Section 10b of the protocol is used to determine the rate of migration of inorganic chemicals (including
metals), non-volatile organic compounds (dissolved organic carbon), and semi-volatile organic
compounds (SVOCs) to environmental waters at environmentally relevant temperatures. This can
provide insight into the solid phase diffusion process. This method, which is designed to enhance the
leaching of materials found at low concentrations in either the solid or liquid and is a modification of
ASTM Method D4874 and EPA Method 1315. EPA may consider updates to protocol 10b in the near
future.
10.7.1. Approach
Migration of chemicals may be controlled in large part by the distance the additive travels from the
interior of the polymer to its surface and is generally considered a partitioning effect based on Fick's law
of diffusion and mass transfer theory. Further, polymers are also fragmented by abrasive and
weathering processes during use and after disposal (Barnes et al, 2009; Rauert et al 2014). Such
fragmentation increases the polymer's surface-to-volume ratio. This reduces the distance through the
polymer particle that additives travel to reach the surface, and may increase their potential release to
the environment.
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This method consists of sample preparation and characterization, leaching through a HPLC column, and
sample analysis.
10.7.2. Materials and Equipment
Laboratory apparatus and supplies that will be necessary for the testing include:
Cryomill for polymer grinding
Jars and stainless still mixing balls for cryomill
Jet Sieve for sieving ground particles
BET surface area analyzer
Glass tubes for BET surface area analyzer
Balance with readability of 0.01 gram
Liquid nitrogen
Nitrogen gas
Methylene chloride or suitable solvent
Quikrete pool filter grade sand; 400-800 nm/20-50 mesh or equivalent
Muffle oven or means of baking at 450 ฐC
Stainless steel HPLC column (e.g., HPLC column; 250 x 10 mm) with stainless steel frit and
polyether ether ketone (PEEK) fittings to permit column reuse.
Inert HPLC tubing
ASTM type 2 water (ASTM, 2011) or other types of high purity laboratory water
pH meter
0.01 M NaOH and 0.1 M HCL solution (pH adjustment)
Environmental chamber for maintaining temperature
1 L glass, pre-cleaned bottles that are either amber or covered with foil
25 mL glass, pre-cleaned bottles that are either amber or covered with foil
Internal standard(s)
Quantitation standard(s)
10.8. Experimental Design:
10.8.1. Sample Preparation Procedure
For reproducible results, polymers should be ground to a standard size range. The particle size range of
ground polymers should be recorded. A particle size range of 53 to 300 urn is suggested. This will
enhance the surface-to-volume ratio, providing for a more consistent basis for testing different
polymers. Most polymers are flexible, making grinding by common techniques impossible. Thus
cryogenic grinding (e.g Retsch Cryomill) should be used to reduce polymer sample size prior to testing.
Due to the deformability and agglomerization of polymer particles an instrument that uses an air jet to
disperse particles (e.g. Retsch Jet Sieve) is recommended for separating particles into the desired size
class.
Surface areas of particles should be determined by the BET (Brunauer, Emmett and Teller) approach.
This method is based on the amount of adsorbate gas (typically nitrogen) that forms a monomolecular
layer on the particle surface at liquid nitrogen temperatures (Bart, 2005;
http://www.particletechlabs.com/services/surface-area-and-pore-size-analysis). The specific surface
area result is expressed in units of area per mass of sample (m2/g).
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This protocol uses a Retsch CryoMill (or similar, Figure 29) for sample grinding, followed by sieving for
selecting 50 - 300 um particles using a Retsch AS200 air jet sieving machine (or similar) suitable for
sieving low density polymers as illustrated in Figure 30.
The general steps for the sample preparation procedure are:
a) Measure the starting concentration of chemical substance in the solid, prior to test.
b) Grind the sample. Ensure at least 1 gram or more of sample is available.
c) Determine the surface area of the particles through the BET approach.
d) Repeat the measurement 3 times
More specific example steps for sample preparation are provided as an example below.
a) Measure the starting concentration of chemical substance in the solid, prior to test.
b) Grind or cut sample. Ensure at least 1 gram or more of sample is available,
c) Tighten the lid on grinding jar and begin the cryogenic grinding, ensuring that liquid nitrogen
at -196 ฐC is circulating through the system throughout the grinding process.
d) Transfer the ground sample from the jar into the air jet sieving machine set to retain 3 the
particle fraction within the size range of 53 to 300 jam.
e) Repeat the grinding and sieving process, compositing the grindings into a single aliquot until
0.5 g of sieved sample is retained.
f) Place composited samples pre-cleaned tubes overnight and dry/degas at 65ฐC under
nitrogen flow.
g) Following the instructions for the BET surface area analyzer, measure the surface area using
a 10-point curve with the relative pressure (of the absorbate to the saturated pressure of
the adsorptive) from 0.05 to 0.5.
h) Repeat each measurement 3 times, refilling liquid nitrogen prior to analyzing each sample.
Figure 29. Retsch Cryomill uses liquid nitrogen to embrittle polymer samples.
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Figure 30. Retsch Jet Sieve for generating particles of discrete size ranges.
Figure 31. Micromeritics Gemini V series BET surface area analyzer
Table 10 below is an example experimental schedule that can be used as a guide. Water temperature
and organic carbon content are expected to impact SVOC migration rates from polymers and are
expected to vary in natural waters. Test temperatures of 20ฐC and 40ฐC are recommended to include
the upper end of temperature ranges for natural fresh and salt waters. Water organic carbon content of
0 and 100 mg/L of humic acid (HA) are recommended to model both treated and natural waters (Aldrich
HA is more hydrophobic than some naturally occurring humic acids, but can be used due to its
commercial availability and consistency). Each experimental condition (combination of parameters)
should be tested in triplicate.
Table 10. Example Experimental Schedule for Migration Rate into Water over Time.
A
B
C
D
Test
Minimum Dry
Water TemperatureO
Water Organic Carbon
position
Mass (g-dry)
(ฐC)
(mg/L Humic Acid)
T01
0.5
20
0
T02
0.5
20
100
T03
0.5
40
0
T04
0.5
40
100
B011
-
20
0
^est position marked B01 is a method blank
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10.8.2. General Leaching Test Procedure
A diagram of the equipment and materials to be used in the leachate generation experiments is shown
in Figure 32.
Sand
Eluent for
analysis
'Microplastics
Incubator
Water Conditions
Temperature
Humic acid content
Source
water
HPLC Pump
Figure 32. General Migration rate into Water test apparatus
The general steps for this procedure are:
a) Bake sand in a muffle oven at 450ฐC overnight (> 12 hours) to remove moisture and organic
matter (Quikrete pool filter grade; 400-800 nm/20-50 mesh or equivalent); further clean
sand by extraction with methylene chloride.
b) Mix 1 g of ground polymer with 8 g clean sand. Extremely hydrophobic test chemicals may
require the use of greater amounts of polymer per column to generate a detectable
chemical concentration in the aqueous effluent. If needed, increase polymer loading in
column (while decreasing sand loading) achieve measureable effluent concentrations.
c) Pack stainless steel column (e.g., HPLC column; 250 x 10 mm) with 0.2 g clean sand,
followed by the polymer sand mixture and top with 0.2 g clean sand. Use polyether ether
ketone (PEEK) fittings to permit column reuse and a stainless steel frit to retain the
polymer/sand mixture. The use of this frit is important to prevent particles from escaping
the column. The frit should be smaller than the particle size of the prepared ground or cut
polymer sample- for example, 2 to 10 |a,m. Most chemical additives are expected to be
present in a polymer at high concentrations relative to the water solubility of the chemical.
The range of water solubility values for the chemical should be compiled and considered. A
new column frit/filter should be used prior to each experiment.
d) Adjust the pH of the water to 7 with 0.01 M NaOH or 0.1 M HCI.
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e) Maintain water temperature by placing the column and a loop of stainless steel tubing
inside an environmental chamber (e.g. Associated Environmental System LH6) capable of
maintaining temperature within +/- 1ฐC.
f) Connect the pump, column and eluent reservoir with stainless steel tubing.
g) Deliver water to the column using a commercially available pump (e.g., Waters 600 HPLC
pump) that possesses an inert fluid pathway.
h) Establish a water flow rate. A flow rate of 1.0 mL/min through the HPLC column is
recommended. Report the water flow rate.
i) Collect eluent in 1 L glass, pre-cleaned bottles that are either amber or covered with foil to
prevent possible additive photo-oxidation.
j) Collect 10 mL samples using a sample collection schedule. A sample collection schedule is
shown in Table 11. Samples are collected by diverting the flow to 25 mL glass, pre-weighed,
pre-cleaned bottles that are either amber or covered with foil to prevent possible additive
photo-oxidations.
k) Weigh 25 mL bottles after sample collection to the nearest 0.01 g.
I) Add surrogate standard to each column eluate sample.
m) Extract each sample with methylene chloride or a suitable solvent.
n) Reduce each sample to 0.5 mL under a stream of high purity nitrogen.
o) Add internal quantitation standard to prepare for analysis.
Table 11. Sample Collection Schedule for Migration Rate into Water over Time.
A
Sample name
B
Sample collection
start time
C
Sample collection end time
1 hr
55 min
65 min
2 hr
115 min
125 min
5 hr
295 min
305 min
1 day
24hr
24hr lOmin
2 day
48 hr
48hr lOmin
3 day
72 hr
72hr lOmin
4 day
96 hr
96hr lOmin
5 day
120 hr
120hr lOmin
6 day
144 hr
144hr lOmin
7 day
168 hr
168hr lOmin
10.8.3. Analytical Procedure
This protocol covers a wide range of chemical substances leaching from samples, which require different
analytical methods. Depending on the chemical, analyzing both the solid and aqueous phase of the
chemical may be of interest. If both phases are analyzed, both phases should be reported. Table 9
provides a list of EPA analytical methods for various chemicals.
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10.8.4. Calculations of leaching rate and mass migrated
10.8.4.1. Calculation of Leaching Rate
The leaching rate of the chemical of concern at given time t during the test is calculated from Equation
10-2:
RL(t) = y(t) X Q (10-2)
where RL(t) = leaching rate at elapsed time t (mg/h)
y(t) = chemical concentration in water sample collected at time t (mg/L)
Q = water flow rate (L/h).
10.8.4.2. Area-specific Leaching Rate
The area-specific leaching rate at elapsed time t is calculated from Equation 10-3:
AL(t) = (10-3)
where AL(t) = area-specific leaching rate at elapsed time t (mg/m2/h)
S = surface area of solid sample exposed to the eluent (m2).
10.8.4.3. Cumulative Mass Leached from Solid Sample
If n water samples are collected during the leaching test and the results are (ti, yi), (t2, y2),... (t, yn), the
cumulative mass of chemical dissolved between elapsed time zero and t can be calculated from
Equation 10-4:
^(0 = Q I.?=i (yi+1+yi)2X (ti+1~ t0 (10-4)
where W(t) = cumulative mass leached from solid sample at elapsed time t (mg)
Q = water flow rate (L/h)
y yi+i = chemical concentrations in water samples /' and /'+1 (mg/L)
t,-, ti+i= sampling times for water samples /' and /'+1 (h).
For example, the cumulative mass dissolved at elapsed time t3 is
w(t3) = q ^+yi)xfe-ti)+^+y2)x(t3-t2) (io_5)
10 8.4.4. Cumulative Mass Release
The cumulative mass released of the chemical of concern is the mass of the chemical dissolved in the
aqueous phase during the leaching test (EPA method 1315), expressed in (mg chemical/kg dry solid
material), as shown in Equation 10-6:
m(t) = ฎ (10-6)
where m(t) = mass release at elapsed time t (mg/kg)
W(t) = cumulative mass leached from solid sample at elapsed time t (mg), from Equation 3.
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Ws = dry mass of test sample (kg).
Note that the leaching rate, and area-specific leaching rate can be calculated for each water sample
taken during the leaching test. The cumulative mass leached from solid sample and cumulative mass
release can be calculated for all water samples except the first sample (ti, yi). Plotting these calculated
rates against the elapsed time will show how rates changed during the duration of the leaching test.
10.9. Reporting of Results and Records Retention:
10.9.1. Records to be Maintained
Records submitted to the EPA should include, but are not limited to, the following:
a. The original signed protocol and any amendments.
b. Identification and characterization of the test substance as provided by Sponsor.
c. Identification and characterization of the material in question.
d. Batch ID of material used in characterization step and of material used in leaching step.
e. Experiment initiation and termination dates.
f. Laboratory log books (e.g., stock solution concentration calculations and solution
preparation, calibration, and QC data).
g. Instrument (e.g., GC/ECNI) data files.
h. Spreadsheet files for data processing.
i. Copy of final report.
10.9.2. Final Report
A final report of the results of the study should be prepared and submitted to the EPA. The final report
should include, but is not limited to the following, when applicable:
a. Name and address of facility performing the study.
b. Dates on which the study was initiated and completed.
c. Objectives and procedures stated in the approved protocol, including any changes in the
original protocol.
d. Identification and characterization of the test substance as provided by sponsor.
e. A summary and analysis of the data and a statement of the conclusions drawn from the
analysis.
f. A description of the transformations and calculations performed on the data.
g. A description of the methods used and reference to any standard method employed.
h. A description of the instrumentation utilized.
i. A description of the preparation of the test solutions, the testing concentrations, and the
duration of the test.
j. A description of sampling and analytical methods, including level of detection, level of
quantification, and references,
k. A description of test specimens and test matrix.
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I. A description of the test results including measured values for individual chemicals of
interest for each matrix,
m. A description of all circumstances that may affect the quality or integrity of the data,
n. The name of the study director, the names of other scientists or professionals, and the
names of all supervisory personnel involved in the study.
0. The signed and dated reports of each of the individual scientists or other professionals
involved in the study, if applicable.
p. The location where the raw data and final report are to be stored,
q. A statement prepared by the Quality Assurance Unit listing the types of instrumental
inspections, calibration certifications, the dates that the study inspections were made and
the findings reported to the Study Director and Management,
r. A copy of all raw data including but not limited to instrumentation output, lab notebooks,
and data sheets, etc.
Specific data that should be reported includes:
a. Date and time at the start of the test.
b. Name of the solid material.
c. Experimental conditions, including water pH and temperature.
d. Ambient temperature during migration.
e. Concentration of chemical substances (leachables) in each leachate collection.
f. Time of each leachate collection.
g. Concentration of chemical substances (leachables) in the starting material.
The minimum set of data that should be reported for each leachate includes:
a. Leachate sample ID.
b. Target L/S (mL/g-dry).
c. Mass of "as tested" solid material used (g).
d. Moisture content of material used (gH2o/g) (if moisture content of sample >10%).
e. Volume of extractant used (mL).
f. Measured final leachate pH.
g. Concentrations of target leachables in leachate.
h. Time of collection of leachate.
1. Analytical QC qualifiers as appropriate.
10.93. Changes to the Final Report
If it is necessary to make corrections or additions to the final report after it has been accepted, such
changes should be made in the form of an amendment issued by the Study Director. The amendment
should clearly identify the part of the study that is being amended and the reasons for the alteration.
Amendments should be signed and dated by the Study Director and Laboratory Quality Assurance
Officer.
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10.9.4. Changes to the Protocol
Planned changes to the protocol should be in the form of written amendments signed by the Study
Director and approved by the sponsor's representative and submitted to EPA using procedures in 40 CFR
790.50. Amendments should be considered as part of the protocol and should be attached to the final
protocol. Any other changes should be in the form of written deviations signed by the Study Director
and filed with the raw data. All changes to the protocol should be indicated in the final report. Changes
to the test standard require prior approval from EPA using procedures in 40 CFR 790.55.
10.10. References:
ASTM (2011). D1193 - 06(2011) Standard Specification for Reagent Water.
https://www.astm.org/Standards/D1193.htm
ASTM. (2014) Method D4874. Standard Test Method for Leaching Solid Material in a Column Apparatus.
http://www.astm.org/Standards/D4874
EPA. (2012) Method 1316. Liquid Solid Partitioning as a Function of Liquid-to-Solid Ratio in Solid
Materials Using a Parallel Batch Procedure, https://www.epa.gov/sites/production/files/2015-
12/documents/1316.pdf
Bart, C.J. 2005. Additives in Polymers: Industrial Analyses and Applications. John Wiley & Sons Ltd. West
Essex, England. 819 p.
Appendix 10-A. Migration into Water Liquid to Solid Ratio
Samples must be dried if the moisture content of sample is greater than 10%. A drying oven should be
used to determine the solids content of the solid material. A small amount of sample (typically 5-10
grams) should be dried at 105ฑ2 ฐC for at least 24 hours until it is at constant mass.
Equation 10A-1 is then used to calculate the solids content:
sc = Mdry [10A-1]
Mtest
Where:
SC = solids content of "as-tested" material (g-dry/g)
Mdry mass of dry material specified in the method (g-dry)
Mtest = mass of "as-tested" solid equivalent to the dry-material mass (g)
Oven-dried samples should be properly discarded and not used for subsequent steps.
The moisture content is then calculated using Equation 10A-2.
MCW = [10A-2]
test
Where:
MCwet = moisture content on a wet basis (gH2o/g)
Calculate and record the amount of "as-tested" material equivalent to the dry mass in Column D of
Table 8 using Equation 10A-3:
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Mtest = [10A-3]
Where:
SC = solids content of "as-tested" material (g-dry/g)
Calculate and record the volume of moisture contained in the "as tested" sample in Column E of Table 1
using Equation 10A-4 :
V Mtest x(1~sc^ MOA 41
VW,sample ~ [1UA-4J
Pw
Where:
Vw, sample = volume of water in the "as tested" sample (mL)
Pw = density of water (1.0 g/mL at room temperature)
Calculate and record the volume of reagent water needed to bring each leaching experiment to the
target L/S in Column F of Table 8 using Equation 10A-5:
VrW Mdry X LS Vw,sample [10A-5]
Where:
VRW = volume of reagent water needed to complete L/S (mL)
LS = liquid-to-dry-solid ratio (mL/g)
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