ASTM D6596-00(2021)

Standard Practice for Ampulization and Storage of Gasoline and Related Hydrocarbon Materials

SIGNIFICANCE AND USE
5.1 Ampulization is desirable in order to minimize variability and maximize the integrity of calibration standards or RMs, or both, being used in calibration of analytical instruments and in validation of analytical test methods in round-robin or interlaboratory cross-check programs. This practice is intended to be used when the highest degree of confidence in integrity of a material is desired.  
5.2 This practice is intended to be used when it is desirable to maintain the long term storage of gasoline and related liquid hydrocarbon RMs, controls, or calibration standards for retain or repository purposes.  
5.3 This practice may not be applicable to materials that contain high percentages of dissolved gases, or to highly viscous materials, due to the difficulty involved in transferring such materials without encountering losses of components or ensuring sample homogeneity.
SCOPE
1.1 This practice covers a general guide for the ampulization and storage of gasoline and related hydrocarbon mixtures that are to be used as calibration standards or reference materials. This practice addresses materials, solutions, or mixtures, which may contain volatile components. This practice is not intended to address the ampulization of highly viscous liquids, materials that are solid at room temperature, or materials that have high percentages of dissolved gases that cannot be handled under reasonable cooling temperatures and at normal atmospheric pressure without losses of these volatile components.  
1.2 This practice is applicable to automated ampule filling and sealing machines as well as to manual ampule filling devices, such as pipettes and hand-operated liquid dispensers.  
1.3 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.  
1.4 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety, health, and environmental practices and determine the applicability of regulatory limitations prior to use.  
1.5 This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for the Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.

General Information

• Status: Published
• Publication Date: 31-Mar-2021
• ICS: 27.060.10 - Liquid and solid fuel burners
• Technical Committee: D02 - Petroleum Products, Liquid Fuels, and Lubricants
• Drafting Committee: D02.04.0A - Preparation of Standard Hydrocarbon Blends

Relations

• Refers: ASTM D6362-98(2018) - Standard Practice for Certificates of Reference Materials for Water Analysis
• Effective Date: 15-Oct-2018
• Refers: ASTM E826-08(2013) - Standard Practice for Testing Homogeneity of a Metal Lot or Batch in Solid Form by Spark Atomic Emission Spectrometry
• Effective Date: 01-Apr-2013
• Refers: ASTM D6362-98(2013) - Standard Practice for Certificates of Reference Materials for Water Analysis
• Effective Date: 01-Jan-2013
• Refers: ASTM D6362-98(2008) - Standard Practice for Certificates of Reference Materials for Water Analysis
• Effective Date: 15-Jul-2008
• Refers: ASTM E826-08 - Standard Practice for Testing Homogeneity of a Metal Lot or Batch in Solid Form by Spark Atomic Emission Spectrometry
• Effective Date: 01-May-2008
• Refers: ASTM D6362-98(2003) - Standard Practice for Certificates of Reference Materials for Water Analysis
• Effective Date: 10-Aug-2003
• Refers: ASTM E826-85(1996)e1 - Standard Practice for Testing Homogeneity of Materials for Development of Reference Materials (Withdrawn 2005)
• Effective Date: 01-Jan-1996

Overview

ASTM D6596-00(2021), "Standard Practice for Ampulization and Storage of Gasoline and Related Hydrocarbon Materials," provides guidance on the secure packaging and long-term storage of gasoline and similar liquid hydrocarbons as calibration standards or reference materials (RMs). This standard practice is designed to minimize variability and maintain integrity when preparing and storing volatile hydrocarbon mixtures, which are essential for calibration of analytical instruments and validation of test methods in laboratories. Both manual and automated ampule filling and sealing processes are addressed, emphasizing the importance of homogeneity, stability, and contamination prevention throughout the procedure.

Key Topics

• Ampulization: The process of transferring volatile hydrocarbon materials into glass ampules under controlled conditions to preserve their chemical integrity and prevent contamination.
• Materials and Equipment: Specification of compatible materials for ampule filling (such as TFE-fluorocarbon tubing and glass pipettes), and recommendations for cleaning procedures to avoid cross-contamination.
• Homogeneity and Stability: Procedures for ensuring uniformity across packaged batches, including guidelines for homogeneity testing and stability assessment to support accurate calibration and long-term retention of RMs.
• Labelling and Documentation: Requirements for labeling each ampule, including product information, lot numbers, and safety warnings, and the provision of certificates conforming to relevant ISO guides.
• Safety and Regulatory Considerations: The standard underscores the importance of adhering to established health, safety, and environmental practices as well as compliance with regulations such as 29 CFR 1910.1200 for hazardous materials.

Applications

• Calibration of Analytical Instruments: Ampulized gasoline and hydrocarbon reference materials are essential for calibrating laboratory instruments, ensuring accurate and reliable results in petrochemical analyses.
• Validation of Analytical Methods: By providing stable and homogeneous RMs, laboratories can effectively validate new or existing analytical test methods, especially when participating in round-robin or interlaboratory studies.
• Long-term Material Retention: The ampulization process allows for the secure archival of calibration standards and controls, enabling future comparisons and quality assurance.
• Quality Assurance in Hydrocarbon Laboratories: Adoption of this standardized practice helps laboratories maintain high confidence in the integrity of their reference materials, supporting consistent measurement results across multiple labs and over extended periods.
• Repository or Retain Samples: Packaging for repository purposes ensures that gasoline and hydrocarbon samples maintain their integrity for regulatory, legal, or investigative requirements.

Related Standards

• ASTM D6362: Practice for Certificates of Reference Materials for Water Analysis.
• ASTM E826: Practice for Testing Homogeneity of a Metal Lot or Batch in Solid Form by Spark Atomic Emission Spectrometry.
• ISO Guide 30: Terms and Definitions Used in Connection with Reference Materials.
• ISO Guide 31: Contents of Certificates of Reference Materials.
• ISO Guide 35: Certification of Reference Materials - General and Statistical Principles.
• ISO/REMCO N280: Homogeneity Testing Procedure for the Evaluation of Interlaboratory Test Samples.
• 29 CFR 1910.1200: Hazard Communication Standard from the U.S. Government.

These related standards help support, define, and clarify procedures outlined in ASTM D6596 regarding reference material preparation, homogeneity assessment, certification, and regulatory compliance in the context of ampulization and storage.

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Keywords: ampulization, gasoline storage, hydrocarbon reference materials, calibration standards, laboratory homogeneity, stability testing, ASTM D6596, fuel sample preservation, hydrocarbon standards, petrochemical calibration.

Standards Content (Sample)

This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for the
Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
Designation: D6596 − 00 (Reapproved 2021)
Standard Practice for
Ampulization and Storage of Gasoline and Related
Hydrocarbon Materials
This standard is issued under the fixed designation D6596; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision.Anumber in parentheses indicates the year of last reapproval.A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope D6362Practice for Certificates of Reference Materials for
Water Analysis
1.1 This practice covers a general guide for the ampuliza-
E826Practice for Testing Homogeneity of a Metal Lot or
tion and storage of gasoline and related hydrocarbon mixtures
Batch in Solid Form by Spark Atomic Emission Spec-
that are to be used as calibration standards or reference
trometry
materials. This practice addresses materials, solutions, or
mixtures, which may contain volatile components. This prac-
2.2 ISO Standards:
tice is not intended to address the ampulization of highly
ISO Guide 30Terms and Definitions Used in Connection
viscousliquids,materialsthataresolidatroomtemperature,or
with Reference Materials
materials that have high percentages of dissolved gases that
ISO Guide 31Contents of Certificates of Reference Materi-
cannot be handled under reasonable cooling temperatures and
als
at normal atmospheric pressure without losses of these volatile
ISOGuide35CertificationofReferenceMaterials–General
components.
and Statistical Principles
ISO/REMCO N280Homogeneity Testing Procedure for the
1.2 This practice is applicable to automated ampule filling
Evaluation of Interlaboratory Test Samples
and sealing machines as well as to manual ampule filling
devices, such as pipettes and hand-operated liquid dispensers.
2.3 Government Standard:
29 CFR 1910.1200Hazard Communication
1.3 The values stated in SI units are to be regarded as
standard. No other units of measurement are included in this
3. Terminology
standard.
3.1 Definitions:
1.4 This standard does not purport to address all of the
safety concerns, if any, associated with its use. It is the
3.1.1 accepted reference value (ARV)—a value that serves
responsibility of the user of this standard to establish appro-
asanagreed-uponreferenceforcomparisonandthatisderived
priate safety, health, and environmental practices and deter-
as: (1) a theoretical or established value, based on scientific
mine the applicability of regulatory limitations prior to use.
principles; (2) an assigned value, based on experimental work
1.5 This international standard was developed in accor-
of some national or international organization, such as the
dance with internationally recognized principles on standard-
National Institute of Standards and Technology (NIST); or (3)
ization established in the Decision on Principles for the
a consensus value, based on collaborative experimental work
Development of International Standards, Guides and Recom-
under the auspices of a scientific or engineering group.
mendations issued by the World Trade Organization Technical
3.1.2 ampule—a glass vessel for the storage of liquid
Barriers to Trade (TBT) Committee.
materials, possessing a long narrow neck for the purpose of
providing a flame-sealed closure.
2. Referenced Documents
2.1 ASTM Standards: 3.1.3 headspace—the unfilled capacity of an ampule that
allows for physical expansion due to temperature and pressure
changesofthefilledmaterialwhilemaintainingtheintegrityof
This practice is under the jurisdiction ofASTM Committee D02 on Petroleum
the package.
Products, Liquid Fuels, and Lubricantsand is the direct responsibility of Subcom-
mittee D02.04.0A on Preparation of Standard Hydrocarbon Blends.
Current edition approved April 1, 2021. Published May 2021. Originally
approved in 2000. Last previous edition approved in 2016 as D6596–00 (2016).
DOI: 10.1520/D6596-00R21. Available fromAmerican National Standards Institute (ANSI), 25 W. 43rd St.,
For referenced ASTM standards, visit the ASTM website, www.astm.org, or 4th Floor, New York, NY 10036, http://www.ansi.org.
contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM AvailablefromU.S.GovernmentPrintingOfficeSuperintendentofDocuments,
Standards volume information, refer to the standard’s Document Summary page on 732 N. Capitol St., NW, Mail Stop: SDE, Washington, DC 20401, http://
the ASTM website. www.access.gpo.gov.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D6596 − 00 (2021)
3.1.4 homogeneity—the uniformity of the characteristics of fundamental issues, namely, assessment of the characteristics
the packaged material across the entire packaging run deter- of the material to be ampulized, sources of contamination,
mined for the purpose of demonstrating the suitability of the sampling of the bulk container, volume dispensing accuracy,
batch for its intended purpose. inert atmosphere blanketing, flame sealing, sequential ampule
labeling, packaging homogeneity sampling, and homogeneity
3.1.4.1 Discussion—There are two homogeneity testing
cases; one in which the material is ampulized as a reference testing. Failure to adequately consider any of the above issues
may negatively impact the quality, consistency, and value of
material at the time of ampulization, and one in which the
material is not. the ampulized material as an RM.
(1) reference material at time of ampulization—The mate-
4.3 Confidence in the homogeneity of the ampulized prod-
rial to be ampulized is a reference material that has accepted
uct can only be established through homogeneity testing,
true or consensus values.Ampulization of a reference material
whichinvolvesthesampling,analysis,andstatisticaltreatment
would require homogeneity testing in order to assess the
of data from randomly selected ampules obtained from the
variability caused by the ampulization process on the true or
beginning, middle, and end of the ampulized lot. Determina-
consensus values for the reference material.
tion of ampulization homogeneity requires that the order in
(2) not a reference material at time of ampulization—The
which the ampules have been filled and sealed be maintained.
material to be ampulized is not a reference material at the time
Homogeneity testing reveals the variability of the product
of ampulization but is intended to have characterization and
introduced during the ampulization process. Homogeneity
assignment of true or consensus values at some future date.
results must be within acceptable limits of the ARV or
Rigidhomogeneitytestingisnotrequiredonsuchamaterialat
consensus value for the RM.
the time of ampulization since the true or consensus values
4.4 Ampulization does not necessarily guarantee sample
have not yet been determined. However, ampules must be
stability or indefinite shelf life of the RM. Initial homogeneity
retained at the beginning, middle, and end of the ampulization
data establish reference values for future tests of sample
process. It is recommended that qualitative testing be done on
stability and determination of shelf life.
at least one sample from each of the beginning, middle, and
end of the ampulization process. The remaining ampules
5. Significance and Use
should then be retained for future homogeneity testing to
determine quantitative or consensus values.
5.1 Ampulization is desirable in order to minimize variabil-
ityandmaximizetheintegrityofcalibrationstandardsorRMs,
3.1.5 reference material (RM)—a material or substance of
or both, being used in calibration of analytical instruments and
which one or more properties are sufficiently well established
in validation of analytical test methods in round-robin or
to enable the material to be used for the calibration of an
interlaboratorycross-checkprograms.Thispracticeisintended
apparatus, the assessment of a method, or the assignment of
tobeusedwhenthehighestdegreeofconfidenceinintegrityof
values to similar materials.
a material is desired.
3.1.6 shelf life—the period of time, under specified storage
conditions, for which the RM will possess the same properties 5.2 This practice is intended to be used when it is desirable
or true values, within established acceptance limits. tomaintainthelongtermstorageofgasolineandrelatedliquid
hydrocarbon RMs, controls, or calibration standards for retain
3.1.7 stability testing—tests required to demonstrate the
or repository purposes.
chemical stability of the ampulized RM for the purpose of
determining the shelf life of the RM.
5.3 This practice may not be applicable to materials that
contain high percentages of dissolved gases, or to highly
4. Summary of Practice
viscous materials, due to the difficulty involved in transferring
such materials without encountering losses of components or
4.1 The physical and chemical characteristics (for example,
ensuring sample homogeneity.
volatility,reactivity,flammability,andsoforth)ofagasolineor
related hydrocarbon mixture is first assessed to determine the
6. Procedure
appropriate procedures for sample handling, sample transfer,
and ampulization. Then a uniform quantity of gasoline or
6.1 Manual Ampule Filling and Sealing:
hydrocarbon mixture is dispensed into suitably sized glass
6.1.1 Apparatus—Devices used for manual filling of am-
ampules (purged with an inert gas), and the ampules are
pules include glass pipettes as well as other types of commer-
flame-sealed with a torch.Anumber of ampules from through-
cially available hand-operated, mechanical, liquid-dispensing
out the filling and sealing process are selected and tested by
devices.
appropriate test methods to determine homogeneity across the
6.1.2 Storage of Bulk Material—Bulk gasoline and similar
lot. Additional ampules are retained for later testing to deter-
liquid hydrocarbon materials must be adequately sealed and
mine stability and shelf life.
stored to prevent loss of volatile components prior to ampuli-
zation. Refrigerated storage in sealed metal drums, barrels, or
4.2 This practice addresses the common difficulties associ-
amber glass containers is recommended.
ated with the ampulization and storage of gasoline and similar
6.1.3 Compatibility of Materials/Sources of Contamination:
liquid hydrocarbon materials, which may contain volatile
components. The process of ampulization, whether performed 6.1.3.1 MaterialsthatcomeincontactwiththebulkRMand
using manual or automated equipment, involves the same its vapors during dispensing must be compatible with the
D6596 − 00 (2021)
gasoline or hydrocarbon material. Glass pipettes are recom- accurately determined volume of RM. The minimum dispens-
mended. Plastic or rubber materials containing phthalates or ing volume for packaging the RM must be known ahead of
other types of plasticizers must be avoided. time.
6.1.3.2 Any part of the dispensing device that comes in 6.1.6.2 Introduce an inert atmosphere into the ampule by
contact with the material, including glass pipettes, hand purging the ampule for a few seconds with nitrogen or other
dispensers, and any necessary connection hardware, must be inert gas immediately prior to filling. A disposable glass
cleaned prior to packaging a different material. Recommended dropperconnectedtoagassourceusingrubbertubingprovides
cleaning procedures involve soaking parts in soapy water, a convenient way of purging the ampule.
rinsing with clean water, followed by methanol or other 6.1.6.3 If using graduated pipettes, introduce a sufficient
suitable solvent, followed by drying under a stream of clean volume of material to the ampule to meet the minimum
nitrogen. dispensing volume requirements for packaging the RM. Note
6.1.4 Assessment of Material to Be Ampulized: that the final dispensed volume at room temperature will be
6.1.4.1 Volatility—Prior to packaging, materials containing affected by the bulk material temperature at the time of
highly volatile components must be cooled sufficiently to dispensing. Therefore, for consistent volume dispensing, the
minimize volatile losses during ampulization. Failure to suffi- temperature of the bulk material must be known and must be
ciently cool the material also may result in difficulty in kept constant during the entire dispensing process.
obtaining effective ampule sealing. The material must not be 6.1.6.4 If other types of nongraduated, manual, filling de-
cooled to temperatures below which the composition of the vices are being used, they must be calibrated. Using Class A
RMwouldbeaffected(forexample,producingprecipitationor glassware or pipettes, measure into an ampule a volume of
solidification). Gasoline may be cooled to –20°C without room temperature water equal to the volume of RM to be
incurring compositional changes. The bulk material must be dispensed. Mark the level on the ampule.
kept cold during the filling process. 6.1.6.5 Make adjustments to the manual dispensing device
6.1.4.2 Reactivity—Consideration should be given to the until 50 consecutive ampules are consistently filled to the
chemical reactivity of the RM being packaged. Gasoline predetermined mark on the ampule.
samples containing olefins and diolefins should be packaged 6.1.6.6 Once volume dispensing adjustments have been
under an inert atmosphere blanket of nitrogen, argon, or other completed,beginfillingampulesfromthebulksupply,keeping
suitable gas. Ampules should be flushed with inert gas imme- the filled ampules cold by placing them immediately into a
diately prior to dispensing of the gasoline. Use of amber glass container that is at a temperature of approximately –20°C.
ampules will minimize photo-oxidation. This may be achieved by using crushed dry ice.
6.1.4.3 Odors—Odorous materials such as gasoline should 6.1.6.7 The ampules should be sealed as soon as possible
bepackagedinawell-ventilatedarea.Thebulkmaterialshould afterfillingtoavoidlossofvolatilecomponents.Ifampulesare
be kept adequately sealed during the ampulization process to being manually sealed, a two person operation, in which one
minimize loss of volatiles. person dispenses the material and a second person seals the
6.1.4.4 Flammability—Ampule sealing requires use of a ampules, is suggested.
flame hot enough to melt glass. Care must be taken in 6.1.6.8 Periodically inspect filled and sealed ampules to
ampulization of highly flammable materials since ampule ensure that the fill volume is maintained throughout the
contents could ignite. Ampules must be kept cold through the packaging run.
sealing step. However, care should be taken to avoid, as much 6.1.7 Ampule Sealing:
as possible, condensation of water inside the ampule. Ampu- 6.1.7.1 Ampules may be flame-sealed by hand, using a
lization is best carried out when the room humidity is low. suitable torch. The flame used must be hot enough to quickly
6.1.5 Sampling of the Bulk Container: soften the neck of the ampule. Propane/air or natural gas/air
6.1.5.1 After bringing the bulk container temperature down flames are sufficient for most applications. Hydrogen/oxygen
to the working temperature, withdraw a minimum of three flames may be required for sealing large, thick-walled glass
samplesfromeachbulkcontainer,usingcleanmanualpipettes. ampules.
Immediately dispense the material into crimp top chromatog- 6.1.7.2 The ampule should be kept cold through the sealing
raphy vials, seal, and label. These samples will be designated process.
as representative of the bulk material and will be used to 6.1.7.3 Tofacilitatesealing,thetorchshouldbemountedon
establish reference values for the homogeneity testing. a stand on a bench top such that both hands can be free to
6.1.5.2 Some vial closures are not suitable for hydrocarbon perform the actual sealing process.
analyses, such as uncoated silicone rubber. Only TFE- 6.1.7.4 Wearing gloves, hold the ampule by the bottom in
fluorocarbon-coated closures should be used. In addition, the one hand and by the neck tip in the other. Alternatively, large
vials should be analyzed as soon as is practical, since no tongs may be used to hold the neck in order to minimize the
crimped vial is completely leak free. risk. The ampule neck is placed into the flame, constantly
6.1.6 Adjusting Dispensing Volume: rotatingtoensureuniformheatingoftheglass.Focustheflame
6.1.6.1 Typically, it is more important to provide a mini- midway between the open end and the breakmark on the
mumdispensedvolumeintheampuleratherthantoprovidean ampule. The flame should never contact the contents of the
D6596 − 00 (2021)
ampule or the direct open end of the ampule. (Warning—For lines. As the bulk container is emptied and the headspace is
safety reasons, if the material being ampulized is flammable, it correspondingly increased, differential vaporization can
is recommended that the volume being ampulized be mini- change the bulk concentration, enriching the high boilers (less
mized.) volatile components) and depleting the low boilers (more
volatilecomponents).Caremustthereforebetakentocomplete
6.1.7.5 After several seconds of exposure to the flame, the
glass should begin to soften. Once the glass is softened, the the ampulization process as expeditiously as is reasonably
possible.
neck may be pulled away from the ampule while still in the
flame, until the glass draws down and forms a seal. The top of
6.2.4.2 Reactivity—Consideration should be given to the
the ampule should be polished by rotating it in the flame until
chemical reactivity of the RM being packaged. Gasoline
a smooth seal is obtained.
samples containing olefins and diolefins should be packaged
6.1.7.6 The seal should be inspected and should be smooth
under an inert atmosphere blanket of nitrogen, argon, or other
and free of any carbon deposits. The thickness of the seal suitable gas. Ampules should be flushed with inert gas imme-
should be comparable to the thickness of the ampule wall. If
diately prior to dispensing of the gasoline. Use of amber glass
the RM contains volatile materials, sealing may be difficult if ampules will minimize photo-oxidation.
the material is not sufficiently cooled. Some problems encoun-
6.2.4.3 Odors—Odorous m
...