Designation: D7754 – 11

Standard Test Method for

Determination of Trace Oxygenates in Automotive Spark-
Ignition Engine Fuel by Multidimensional Gas
Chromatography1
This standard is issued under the fixed designation D7754; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.

1. Scope priate safety and health practices and determine the applica-
1.1 This test method covers the determination of trace bility of regulatory limitations prior to use.
oxygenates in automotive spark-ignition engine fuel. The 2. Referenced Documents
method used is a multidimensional gas chromatographic
method using 1,2-dimethoxy ethane as the internal standard. 2.1 ASTM Standards:2
The oxygenates that are analyzed are: methyl-tertiary butyl D4057 Practice for Manual Sampling of Petroleum and
ether (MTBE), ethyl-tertiary butyl ether (ETBE), diisopropyl Petroleum Products
ether (DIPE), methanol, tertiary-amyl methyl ether (TAME), D4307 Practice for Preparation of Liquid Blends for Use as
n-propanol, i-propanol, n-butanol, i-butanol, tert-butyl alcohol, Analytical Standards
sec-butyl alcohol, and tert-pentanol. Ethanol is usually not D4815 Test Method for Determination of MTBE, ETBE,
measured as a trace oxygenate since ethanol can be used as the TAME, DIPE, tertiary-Amyl Alcohol and C1 to C4 Alco-
main oxygenate compound in finished automotive spark- hols in Gasoline by Gas Chromatography
ignition fuels such as reformulated automotive spark-ignition D6304 Test Method for Determination of Water in Petro-
fuels. The concentration range of the oxygenates covered in the leum Products, Lubricating Oils, and Additives by Coulo-
ILS study was from 10 µg/Kg to 2000 µg/Kg. In addition this metric Karl Fischer Titration
method is also suitable for the measurement of the C5 isomeric 3. Terminology
alcohols (2-methyl-1-butanol, 2-methyl-2-butanol) present
from the fermentation of ethanol. 3.1 Definitions of Terms Specific to This Standard:
1.2 The ethanol blending concentration for which this test 3.1.1 electronic pressure control, n—electronic pneumatic
method applies ranges from 1 to 15% by volume. Higher control of carrier gas flows. Can be flow or pressure pro-
concentrations of ethanol coelute with methanol in the analyti- grammed to speed up elution of components.
cal column. Lower levels of ethanol, similar to the other 3.1.2 flame ionization detector (FID), n—detector used to
oxygenate, can be calibrated and analyzed also. If higher analyze the components eluting from the column.
ethanol concentrations are expected, the window cutting tech- 3.1.3 fluidic switch, n—device that reverses the directional
nique can be used to avoid ethanol from entering the analytical flow in a union T altering the pressure at the midpoint. In its
column and interfere with the determination of the other simplest design it is also known as a Dean Switch.
oxygenates of interest. Refer to Appendix X1 for details. 3.1.4 inlet, n—capillary split/splitless inlet system operated
1.3 The values stated in SI units are to be regarded as in the split mode is recommended. Operate the inlet within its
standard. No other units of measurement are included in this linear range.
standard. 3.1.4.1 split ratio, n—in capillary gas chromatography, the
1.3.1 Alternate units, in common usage, are also provided to ratio of the total flow of carrier gas to the sample inlet versus
increase clarity and aid the users of this test method. the flow of the carrier gas to the capillary column is expressed
1.4 This standard does not purport to address all of the by:
safety concerns, if any, associated with its use. It is the Split ratio 5 ~S 1 C!/C (1)
responsibility of the user of this standard to establish appro-
where:

1
This test method is under the jurisdiction of ASTM Committee D02 on
2
Petroleum Products and Lubricants and is the direct responsibility of Subcommittee For referenced ASTM standards, visit the ASTM website, www.astm.org, or
D02.04.0L on Gas Chromatography Methods. contact ASTM Customer Service at [email protected]. For Annual Book of ASTM
Current edition approved Oct. 1, 2011. Published November 2011. DOI:10.1520/ Standards volume information, refer to the standard’s Document Summary page on
D7754–11 the ASTM website.

Copyright (c) ASTM International. 100 Barr Harbor Drive, P.O. Box C700 West Conshohocken PA United States

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D7754 – 11

S = flow rate at the splitter vent, and ration A (Fig. 1), only the components eluting from the
C = flow rate at the column outlet. analytical column are analyzed. In the two detector Configu-
3.1.5 low volume connector, n—special union for connect- ration B (Fig. 2), detector one is used to monitor the apolar
ing two lengths of tubing 1.6-mm inside diameter and smaller. elution and aid in setting “heart-cut” times for specific oxy-
Sometimes this is referred to as zero dead volume union. genates while the second detector is used to monitor the
3.1.6 multidimensional gas chromatography, n—gas chro- analytical column elution and also for the quantitation of the
matographic technique where using hardware (valves, pressure oxygenates. The second detector response is proportional to the
switches, etc.) in which selected components from one column oxygenates and DME components concentration. The signal is
(primary column) are transferred to a secondary column recorded, the peak areas are measured, and the concentration of
differing in characteristics (film thickness, polarity, capacity, each oxygenate is calculated with reference to the internal
etc.) from the first column. standard.
3.1.7 ppm, n—parts per million, or micrograms per gram 4.3 Alternatively, a fluidic switching system, Configuration
(mg/kg). C (Figs. 3 and 4) may be used instead of valve switching. In
3.1.8 WCOT column, n—wall-coated open tubular, a type of this system, the two columns are joined by a zero dead volume
capillary gas chromatographic column prepared by coating the (ZDV) tee purged by an auxiliary carrier source. At injection,
inside of the capillary wall with a specified thin film of the auxiliary flow is low, and the inlet flow is sufficient so that
stationary phase. The coatings used are either 100% polydim- at the midpoint where the two columns join, the flow is the
ethyl siloxane or 5% phenyl-polydimethylsiloxane. required flow to transfer the oxygenates to the PLOT column.
3.1.8.1 apolar column, n—polydimethylsiloxane nonpolar Thus, there is forward flow through the pre-column and the
column used as a pre-column. analytical column. Once the oxygenates have passed through to
3.1.8.2 PLOT column-oxygen selective, n—porous-layer the analytical column, the inlet flow is decreased and the
open tubular which is an oxygenate selective capillary gas- auxiliary flow is increased, which results in backflushing the
solid chromatographic column. It is used as an analytical pre-column through the split vent of the front inlet while the
column. analytical column continues the separation.

4. Summary of Test Method 5. Significance and Use

4.1 An appropriate internal standard of a product that is not 5.1 The analysis of trace oxygenates in automotive spark-
present in refinery streams, such as 1,2-dimethoxy ethane ignition engine fuel has become routine in certain areas to
(1,2-DME), is added to the sample, which is then introduced ensure compliance whenever oxygenated fuels are used. In
into a gas chromatograph equipped with two columns and a addition, test methods to measure trace levels of oxygenates in
4-port switching valve. The sample first passes onto an apolar automotive spark-ignition fuel are necessary to assess product
(non-polar) polydimethylsiloxane WCOT column that per- quality.
forms a pre-separation of the trace oxygenates and elutes
unwanted high boiling hydrocarbons to vent. The oxygenates 6. Apparatus
and the DME are transferred to the analytical oxygen selective 6.1 Chromatograph—A multidimensional gas chromato-
column by the switching valve. While the oxygenates and the graphic system, which is able to adequately resolve oxygenates
DME are eluting from the analytical column, the inlet’s carrier and an internal standard and to eliminate hydrocarbon, as well
gas is used to elute the hydrocarbons from the pre-column to as other interferences, is used for these analyses. The instru-
yield a stable baseline for the next analysis. The auxiliary ment is to be configured to operate using the approximate
pressure controller is used to provide carrier gas to the conditions listed in Table 2. The system requires a column
analytical column during the analysis. switching mechanism equivalent to Fig. 1 or Fig. 2 if using a
4.2 The eluted components Table 1 are detected by one or valve system. If using a fluidic system then the fluidic switch
two flame ionization detectors. In the single detector Configu- and auxiliary flow control are required as shown in Fig. 3 and

TABLE 1 Component List with Retention and Calibration Characteristics for WCOT/PLOT Column Set Using Conditions of Table 2A
Component RT (min) Mol Wt BP (°C) Slope y-Int Corr. Coef.
ETBE 12.7 102.2 70 to 72 1.919 -0.02 0.999
MTBE 12.8 88.2 55 to 56 1.689 0.01 0.999
DIPE 12.9 102.2 68 to 69 2.124 -0.06 0.999
TAME 13.6 102.2 85 to 86 2.023 -0.02 0.999
Methanol 15.6 32.0 65 0.779 -0.09 0.997
Ethanol 18.7 46.1 78 1.352 0.19 0.999
iso-Propanol 22.2 60.1 81 to 83 1.504 -0.06 0.999
n-Propanol 22.2 60.1 97 ... ... ...
t-Butanol 23.8 74.1 82 1.951 -0.12 0.999
s-Butanol 23.8 74.1 98 ... ... ...
iso-Butanol 23.8 74.1 117 ... ... ...
n-Butanol 24.4 74.1 118 1.906 -0.05 0.999
tert-Pentanol 25.1 88.1 102 2.148 -0.04 0.998
1,2-DME 26.0 90.1 85 ... ... ...
A
For coeluting compounds the response is assigned to the first peak listed. Values may be different for different instruments.

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D7754 – 11

FIG. 1 Schematic of Chromatographic System—Configuration A

FIG. 2 Schematic of Chromatographic System—Configuration B

FIG. 3 Fluidic Switch Schematic—Oxygenate Transfer

Fig. 4. Carrier gas flow controllers (EPC) shall be capable of The system shall have sufficient sensitivity and stability to
precise control where the flow rates are low. Pressure control obtain a signal-to-noise ratio of at least 5 to 1 for a 1 ppm
devices and gages shall be capable of precise control for the (m/m) concentration of any oxygenate. In the fluidic system
typical pressures required. only one detector is used.
6.1.1 Detector—Two-flame ionization detectors are prefer- 6.1.2 Switching Valve—A switching valve, to be located
ably used (Configuration B), although the analysis can be within the gas chromatographic column oven or separate oven,
performed using only one detector (Configuration A and C). capable of performing the functions described in 9.2 and

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D7754 – 11

FIG. 4 Fluidic Switch Schematic—Pre-column Backflush

TABLE 2 Chromatographic Conditions

Configuration Switching Valve Fluidic Switch
Carrier Gas Helium Helium
Injection Volume 1.0 µL 1.0 µL
Inlet: Split/Splitless (Split mode) Split/Splitless (Split mode)
Temperature 250°C 250°C
Split Ratio 10:1 10:1
PressureA 7.5 psi, Constant Pressure 2.58 psi, Flow Program Mode
Columns and Flows
Pre-column 30 m by 0.53 mm by 5.0 µm PDMS 15 m by 0.53 mm by 1.5 µm 5% phenyl PDMS
7.5 mL/min @ 60°C Initial Flow: 5.4 mL/min @ 60°C
Hold for 1.5 min
Ramp: 90 mL/min to -5 mL/min
Hold until end of run
Analytical Column 10 m by 0.53 mm by 10 µm Oxygen Selective 10 m by 0.53 mm by 10 µm Oxygen Selective
7.5 mL/min@ 60°C 7.0 mL/min constant flow
Oven:
Initial Temperature 60°C 60°C
Initial Hold 6.0min 6.0min
Ramp 1 10°C/min 10°C/min
Final Temperature 150°C 150°C
Final Hold 5.0 min 5.0 min
Ramp 2 10°C/min 10°C/min
Final Temperature 220°C 220°C
Final Hold 3.0 min 3.0 min
Total Time 30 min 30 min
Detector: FID FID
Temperature 275°C 275°C
Hydrogen 40 mL/min 40 mL/min
Air 450 mL/min 450 mL/min
Make-up (N2) 10 mL/min 10 mL/min
Valve Temperature 150°C N/A
Auxiliary Pressure 10.6 psi 1.50 psi
Vent Restrictor ~30 by 1⁄16 by 0.010 in. SSt N/A
Default Valve Times (for complete analysis):
Initial OFF N/A
0.50 min ON N/A
4.50 min OFF N/A
A
For Configuration A valve timing determination, 9.2, set the inlet pressure to ~5 psi.

illustrated in Fig. 1. The valve shall be of low volume design description. Additional flow source is required as well as
and not contribute significantly to chromatographic deteriora- hardware, which is located in the oven for the column
tion. Alternatively a Deans switching arrangement can also be connection.
used as shown in Figs. 3 and 4. 6.1.2.3 Some gas chromatographs are equipped with an
6.1.2.1 A commercially available valve: 1.6-mm fittings, auxiliary oven, which can be used to contain the valve at an
0.75 mm ports was used in the method development. An isothermal temperature. In such a configuration, the two
equivalent valve may be used. capillary columns are located in the main oven and connected
6.1.2.2 Fluidic Switch, as an option to the two-position to the valve by using low dead volume and inert stainless steel
Switching Valve. See 4.3, Table 2, and Figs. 3 and 4 for a tubing terminated in the GC oven.

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D7754 – 11
6.1.2.4 An automatic valve switching device is used to described in 6.3.1 and which separation efficiency is illustrated
ensure repeatable switching times. Such a device is synchro- in Figs. 5 and 6 can be used.
nized with injection and data collection times. For the pressure 6.3.2.1 LowOx or GS OxyPLOT Polar Analytical
switching approach, automatic precise and stable pressure Column—10 m long by 0.53-mm inside diameter fused silica
control shall be used. Fluidic systems require both a fluidic PLOT column with a 10-µm film thickness. These columns
switch and a programmable auxiliary pressure source to were used in the method development to provide the precision
maintain and program flows. and bias data referred to in Section 14.
6.1.3 Injection System—The chromatograph is to be
equipped with a heated splitting-type inlet device containing a 7. Reagents and Materials
replaceable glass deactivated liner (single-taper style) with 7.1 Gases:
deactivated glass wool at the bottom to retain non-vaporized 7.1.1 Helium, carrier gas, a minimum purity of 99.995% is
components). Split injection is necessary to maintain the actual required. Oxygen scrubbers are recommended to safeguard the
chromatographed sample size within the limits of column and WCOT columns.
detector efficiency and linearity. 7.1.2 For the FID, hydrogen (99.9995% with air as the
6.1.3.1 A microliter automatic syringe injector is used for remainder) and nitrogen (99.995%, as make up) are used.
introducing representative samples into the gas chromato- (Warning—Observe high pressure precautions with all com-
graphic inlet and for adequate repeatability. pressed gases. Observe flammable gas precautions with hydro-
6.2 Data Acquisition System: gen.)
6.2.1 Computer—A data acquisition system containing a 7.2 Standards for Calibration and Identification—
computer and data acquisition software is required. Standards of oxygenates and the internal standard are required
6.2.2 Integrator—Alternatively, an integrator can be used to for establishing identification by retention time as well as
measure peak areas and to perform the analytical calculations. calibration for quantitative analysis. These materials shall be of
6.3 Column Class: known purity and free of the other components to be analyzed.
6.3.1 Apolar (Non-polar) Pre-Column—This column per- (Warning—These materials are flammable and can be harmful
forms a pre-separation of the oxygenates and internal standard or fatal if ingested or inhaled.). The following oxygenates:
from hydrocarbons in the same boiling point range. Unless a ethanol, methyl-tertiary butyl ether (MTBE), ethyl-tertiary
separate auxiliary oven is provided for it, the apolar column butyl ether (ETBE), diisopropyl ether (DIPE), methanol,
shall perform at the same temperature as the polar column tertiary-amyl methyl ether (TAME), n-propanol, i-propanol,
does. n-butanol, i-butanol, tert-butyl alcohol, sec-butyl alcohol, and
6.3.1.1 WCOT Methyl Silicone Pre-Column—30 m long by tert-pentanol are to be used with the highest purity available
0.53 mm inside diameter fused silica column with a 5-µm film (98-99%). Ethanol is usually not measured as a trace sample
thickness of cross-linked polydimethylsiloxane. With fluidic component.
switch (Configuration C) a 30 m long by 0.53 mm with a 1.5 7.3 Iso-octane, or 2,2,4-Trimethylpentane—Used for prepa-
µm 5% phenyl polydimethyl siloxane is recommended. ration of calibration standards and dilution of automotive
6.3.2 Polar Analytical Column—Any column with equiva- spark-ignition fuel samples. In some cases, cyclohexane may
lent or better chromatographic efficiency and selectivity to that be used provided it meets all of the requirements of the

FIG. 5 Oxygenate Elution Pattern, from WCOT Pre-column Only

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D7754 – 11

NOTE—Calibration Standard—250 ppm oxygenates, 7.5% ethanol, and 200 ppm internal standard in iso-octane.
FIG. 6 Oxygenate Elution Pattern from WCOT/PLOT Column Set Using Conditions in Table 2

method. Using cyclohexane, since it elutes in the cut window the system can be assembled with no modifications to deter-
of the oxygenates, may cause difficulty in finding individual mine the cut times from the pre-column.
cut times (see Appendix X1). (Warning—Iso-octane and 9.1.1 Figs. 1 and 2 are plumbing schematics for using a
cyclohexane are flammable and may be harmful if inhaled. commercially available switching valve. This system is de-
High concentrations may cause unconsciousness or death). scribed primarily in the following sections–Configurations A
7.4 1,2-Dimethoxyethane (1,2-DME or ethylene glycol dim- and B.
ethyl ether)—Used as the internal standard. Use Reagent or 9.1.2 Figs. 3 and 4 are the plumbing schematics for using a
Chromatography grade. commercially available fluidic switching system.
9.2 Configuration A (Single Detector Configuration):
8. Sampling 9.2.1 Assembly—Refer to Fig. 1. First connect the polydim-
8.1 Every effort should be made to ensure that the sample is ethylsiloxane pre-column (6.3.1) to the detector directly to set
representative of the finished automotive spark-ignition fuel the cut time (9.2.4) using low-volume connectors and inert
from which it is taken. The use of multiple samples that are narrow bore tubing. It is important to minimize the volume of
mixed or composite sampling is recommended. The use of the chromatographic system that comes in contact with the
epoxy-lined cans are recommended for storage or shipping of sample; otherwise, peak broadening will occur.
the sample, or both. Follow the recommendations of Practice 9.2.2 Vent Restrictor—The vent restrictor is intended to
D4057, when obtaining samples from bulk storage or pipelines. simulate the restriction caused by the PLOT column on the
Samples that contain free layer of water will require special pre-column. This is needed to ensure accurate cut time deter-
treatment. For the latter samples, it may be necessary to mination while the valve is in the OFF position. A piece of
separate and analyze the water and hydrocarbon phases sepa- stainless steel tubing, 30 by 1⁄16 by 0.010 in. I.D., will
rately. The water phase may be determined from a separate approximate the resistance.
method. For such analysis, it is necessary to know the amount 9.2.3 Conditions—Establish the operating conditions listed
of water and hydrocarbon phases to determine a total methanol in Table 2. This gives example conditions for the columns
content for the sample. systems used in the development of this method. With the
8.2 Prior to analysis, allow the sample container as received pre-column connected to the FID directly, the inlet pressure
to equilibrate to ambient temperature. should be adjusted to ~4.5psi. This will set the column flow to
approximately 6.8 mL/min at 60°C. This is necessary since
9. Preparation of Apparatus and Establishment of there is no simulation for the restriction caused by the PLOT
Conditions column when the pre-column is installed directly to the FID.
9.1 Determine Configuration—Refer to 4.2 to determine Modifications to column lengths etc. may require different
which configuration the chromatographic system is designed operating conditions. Check the system for leaks before pro-
for the analysis. For a valve configuration the dual detector ceeding further. Condition the system overnight before pro-
Configuration B (Fig. 2) is recommended due to the fact that ceeding.

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D7754 – 11
9.2.4 Setting Valve Times—Once Configuration A is set up 9.4.1 The pre-column and the analytical column are linked
and the pre-column is connected to the detector, determine the by fluidic switch (CFT) purged union (see Fig. 3). The Inlet
retention time of the oxygenates through the pre-column. EPC delivers 5.4 mL/min to both columns. The Aux EPC
9.2.5 Inject 1 µL of a ~300 ppm solution without ethanol or delivers 1.6 mL/min to the Capillary Flow Technology (CFT)
internal standard. To prepare this, add 20 µL of the solution union. This increases the flow to the analytical column to 7.0
made in 10.3 to 5 mL of iso-octane. Record the chromatogram, mL/min. Under these conditions the oxygenates are transferred
and identify the peaks for each oxygenate using Fig. 5. From in about 1.5 min.
this retention time data, set the oxygenate transfer valve time 9.4.2 High boiling point compounds are retained in the
ON to 0.5 min before the methanol starts eluting, and valve pre-column. Oxygenates and low boiling point hydrocarbons
time OFF to 0.5 min after the TAME peak returns to baseline. elute into analytical column. Oxygenates are trapped at the
The times should be incorporated into the analysis method front of the analytical column. After TAME has eluted to the
before calibration is begun. analytical column, the pre-column flow is reversed.
9.2.6 Reassemble the system by reinstalling the PLOT 9.4.3 Inlet EPC flow is reduced to 4 mL/min (Fig. 4) and
column to the diagram in Fig. 1 and Table 2 using low-volume AUX EPC flow is increased to 11 mL/min. Gas flow through
connectors and inert narrow bore tubing. It is important to the Fluidic Switch backflushes the pre-column in order to send
minimize the volume of the connections into and from the high boiling compounds out the front inlet split vent. Oven
valve. Proceed to place the Valve in the ON position so that the temperature program begins and oxygenates are separated on
apolar column and PLOT column are in series. Inject the the analytical column. A typical chromatogram using this
sample as described in 9.2.5 and leave the valve in the ON system is shown in Fig. 7.
position as determined in 9.2.5. Using the times determined in 9.5 Verification of Detectability—Inject a 5 ppm (wt/wt)
9.2.5 transfer the oxygenates to the PLOT column. calibration solution and ensure that a signal/noise level of at
least 5 is observed. Adjustment of the split ratio may be needed
9.3 Configuration B (Dual Detector Configuration):
depending on the detector. See Fig. 8. The peaks for this level
9.3.1 Assembly—For Configuration B, connect the WCOT (5 ppm m/m) have a height of about 2 pA.
and PLOT columns to the valve system as shown in Fig. 2
9.6 Conditioning—To protect the PLOT column, avoid
using low-volume connectors and inert narrow bore tubing. It
injecting samples until the valve times are properly optimized
is important to minimize the volume of the chromatographic
using calibration standards. It is recommended that when all of
system that comes in contact with the sample; otherwise, peak
the analyses are completed, the GC oven temperature be
broadening will occur. maintained at 220°C, with the pre-column carrier head pressure
9.3.2 Vent Restrictor—The vent restrictor is intended to maintained at 20 psi using the electronic pressure controller for
simulate the restriction caused by the PLOT column on the at least several hours. This procedure conditions the PLOT
pre-column. This is needed to ensure accurate cut time deter- column, which may trap carrier gas contaminants at the normal
mination while the valve is in the OFF position (see Fig. 2). A 60°C starting temperature, and also elute residual heavy
piece of stainless steel tubing, 30 by 1⁄16 by 0.010 in. I.D., will hydrocarbons from the pre-column. Periodically 25 cm can be
approximate the resistance. cut off from the front of the polydimethylsiloxane column to
9.3.3 Conditions—Establish the operating conditions listed remove heavy non-volatiles. The frequency can be determined
in Table 2. This gives example conditions for the columns from the analysis of quality control samples, by evaluating the
systems used in the development of this test method. Modifi- QC results (see Section 13) and also from chromatographic
cations to column lengths etc. may require different operating performance, such as peak tailing etc.
conditions. Check the system for leaks before proceeding
further. Condition the system overnight before proceeding at an 10. Calibration and Standardization
oven temperature of 200°C. 10.1 Preparation of Calibration Standards—Prepare multi-
9.3.4 Setting Valve Times—With the valve in the OFF component oxygenate calibration standards by mass in accor-
position determine first the retention time of the oxygenates dance with Test Method D4307. Prepare a minimum of 5
through the apolar. Subsequently the same is repeated but with calibration standards spanning the range of approximately 10
the valve in the ON position. to 1000 ppm (mass/mass) of each oxygenate and a constant 250
9.3.5 Switch the valve to the OFF position to monitor the ppm of internal standard in iso-octane. Standard concentrations
pre-column only. Inject 1µL of a ~300 ppm solution without should bracket the range of oxygenate concentrations expected.
ethanol or internal standard. To prepare this, add 20µL of the Four stock solutions are prepared to use in the preparation of
solution made in 10.3 to 5 mL of iso-octane. Record the the final calibration solutions: an 8.3% (A), a 10000 ppm (B)
chromatogram. Identify the peaks for each oxygenate using and a 1000 ppm oxygenate solution (C) as well as a 2500 ppm
Fig. 5. From this retention time data, set the oxygenate transfer internal standard solution (D). Ethanol is not included here but
valve time ON to 0.5 min before the methanol starts eluting, can be added to the analyte list if the stream to be analyzed
and valve time OFF to 0.5 min after the TAME peak returns to does not contain the component and trace amounts are to be
baseline. The times should be incorporated into the analysis determined.
method before calibration is begun. 10.2 Before preparing the standards, determine the purity of
9.4 Configuration C (Single Detector Configuration Using a iso-octane reagent and each oxygenate to make corrections for
Fluidic Switch System: the impurities found. Whenever possible, use stocks of at least

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D7754 – 11

NOTE—Conditions in Table 2. Calibration Standard – ppm internal standard in iso-octane.

FIG. 7 Oxygenate Elution Pattern from WCOT/PLOT Column Set Using the Fluidic Switch System

FIG. 8 Signal to Noise Verification—5 ppm Oxygenate/1.0% Ethanol Calibration Standard with Conditions of Table 2.

of 99.9 % purity. Correct the purity of the components for the weight to the nearest 0.1 mg. Fill to the mark with
water content, determined by Test Method D6304. iso-octane and record the weight. Calculate the concentration
10.3 Oxygenate Stock Solution A—Add 3 mL of each of the of each oxygenate using Eq 3 (~10 000 ppm).
12 oxygenates listed in 7.2 in a capped 50 mL bottle or ppm of component i 5 W%i 3 ~Mi / Mt! 3 10 000 (3)
equivalent container. Record the weight to the nearest 0.1 mg.
Do not include the internal standard, 1,2-DME, or the ethanol
at this point. This solution will have each oxygenate at ~8.3 W%i = weight% of component i in 10.3 (%),
wt%. Calculate the weight % using Eq 2. Mi = mass of solution prepared in 10.4 (g), and
Weight % 5 mass of component i ~g! / total mass of solution ~g! 3 100
Mt = total mass of solution in 10.4 (g)
(2) 10.5 Oxygenate Stock Solution C—For levels 100, 50, and
10.4 Oxygenate Stock Solution B—For levels 1000, 500, 10 ppm. In a tarred 100 mL volumetric flask, add 1.2 mL of the
and 250 ppm. In a tarred 100 mL volumetric flask, add 12 mL Oxygenate Stock Solution A prepared in 10.3 and record the
of the Oxygenate Stock Solution A prepared in 10.3 and record weight to the nearest 0.1 mg. Fill to the mark with iso-octane

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D7754 – 11
and record the weight. Calculate the concentration of each 10.8 Store capped stock solutions and calibrations solutions
using Eq 3 (~1000 ppm). below 5°C when not in use.
10.6 Internal Standard Working Solution D—First prepare a 10.9 Standardization:
~5% solution by adding 5 mL 1,2-DME to a tarred 100 mL 10.9.1 Cut Time Determination and Identification—In order
volumetric flask. Record the weight to the nearest 0.1 mg. Fill to insure that the intended oxygenates enter the PLOT column
the flask to the mark with iso-octane and record the weight. it is necessary to determine the retention time through the
Calculate the concentration of DME using Eq 4. Then, in apolar pre-column. This easily accomplished by using the
another 100 mL flask, add 4 mL of this solution, record the solution of the oxygenates prepared in iso-octane as described
weight, and dilute to the mark with iso-octane and record the in 10.4. If the system has 2 detectors as described as Configu-
weight again. Calculate the concentration of this solution D ration B, inject the iso-octane solution in the apolar column
using Eq 5 (~2500 ppm). only. Verify that all the oxygenates have eluted prior to the
Weight% of DME ~W%DME ! 5 mass of DME ~g! / Mt ~g! 3 100 iso-octane. Note the time for the complete elution of TAME.
(4) This will be your cut time. For Configuration A, remove the
PLOT column and install the restrictor to the FID. Inject the
ppm of DME Stock 5 W%DME 3 ~MDME / MDMET! 3 10 000 (5)
sample as described in 9.2.5 and 9.3.5. After the system cut
times are established, determine the retention times of the
W%DME = weight % of first DME 5% solution (%), oxygenates and internal standard using a calibration solution.
MDME = mass of first DME 5% solution (g), and After the determination of the cut time restore the system so
MDMET = total mass of solution (g). that the columns are initially in series. Fig. 5 shows the elution
10.7 Preparation of Calibration Standards: order in the apolar column while Fig. 6 shows the complete
10.7.1 Stock Calibration Solutions—Table 3 gives an ex- oxygenate mixture separated in the combined apolar and PLOT
ample of volumes for preparation of working standards derived column.
from the stock solutions for a set of oxygenate calibration 10.9.1.1 Optimize chromatographic conditions to obtain
standards consisting of 10, 50, 100, 250, 500, and 1000 ppm complete separation of the first three eluting peaks, that is,
(m/m). The standards assume ethanol is present in the streams ETBE, MTBE and DIPE. Maximum resolution of these peaks
to be analyzed in percent levels so the calibration for ethanol is critical for accurate quantification of each individual com-
consists of 1.0, 2.5, 5.0, 7.5, 10 and 15% (m/m). PPM levels of ponent. Difficulties were noted during the Interlaboratory
ethanol, similar to the other oxygenates, can be calibrated and Study of the separation of these three peaks. Suggestions for
analyzed for. the proper resolution of these three peaks are given in
10.7.2 Concentration Determination—Use Eq 6 to calculate Appendix X2.
the concentration in ppm (mg/kg) for each component, includ- 10.9.1.2 Retention Time Shifts—Due to the peak shape and
ing the internal standard, in each solution. The concentration of elution characteristics associated with a PLOT column, the
ethanol can be determined from the % levels calculated in retention time of ethanol will vary from approximately 16 to 18
Table 3. min depending on the concentration. It should also be noted
ppm of component i 5 Ci 3 ~Mi / Mt! (6)
that the peaks eluting before ethanol could also shift slightly
depending on the concentration of ethanol. For accurate
identification of these early eluting peaks, compare the sample
Ci = concentration, ppm, of i in stock solution, with a calibration standard with similar ethanol concentration.
Mi = mass of stock solution added (g), and See Fig. 9.
Mt = total mass of solution (g). 10.9.1.3 Coelutions—Two sets of coeluting peaks are ob-
10.7.3 Working Calibration Solutions—In a 10 mL volu- served with the PLOT column. The first is normal and
metric flask, add 1 mL of the Internal Standard Working iso-propanol. This has been seen to be partially resolved in
Solution D prepared in 10.6 and record the weight. Fill to the some cases but calibration is difficult and so it is recommended
mark with one of the calibration solutions prepared in 10.7.1 the peaks be integrated together and summing their concentra-
and record the weight. This solution is injected using the tions for calibration. The other set is the tertiary, secondary, and
conditions described in Table 2. iso-butanols. Treat these as one peak for integration and sum
10.7.4 Reapply Eq 6 to account for the dilution with internal their concentrations for calibration as C4 alcohols. Refer to
standard. These concentrations will be used in the calibration Table 4 for relative response factors to aid in determining the
tables created. error associated with this technique.

TABLE 3 Preparation of Stock Calibration Solutions

Oxy / EtOH Concentration Oxy Stock B (mL) Oxy Stock C (mL) EtOH, neat (mL) Diluent, I-C8 (mL) Total Vol (mL)
1000 ppm / 15% 11.00 ... 15.00 74.00 100
500 ppm / 10% 5.50 ... 10.00 84.50 100
250 ppm / 7.5% 2.75 ... 7.50 89.75 100
100 ppm / 5% ... 11.00 5.00 84.00 100
50 ppm / 2.5% ... 5.50 2.50 92.00 100
10 ppm / 1.0% ... 1.10 1.00 97.90 100

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NOTE—500 ppm Oxy/10% EtOH standard and 250 ppm Oxy/7.5% EtOH standard overlaid.
FIG. 9 Retention Time Shift—Dependent on Ethanol Concentration

TABLE 4 Coelutions and Estimation of Error Determination

Component RRFA SlopeB % Difference
Iso-Propanol 1.2433 1.4952 16.8
n-Propanol 1.6044 ... 7.3
iso-Butanol 1.9050 1.9512 2.4
tert-Butanol 1.8976 ... 2.7
sec-Butanol 1.6678 ... 14.5
A
Relative Response Factor relative to DME calculated from Test Method D4815 data.
B
From the Linear Least Squares Fit Eq 9 calibration curve data.

10.9.1.4 Possible Interferences—Certain aldehydes and ke- 10.9.3 Linear Least Squares Fit—For the calibration data
tones will elute near the components of interest. Also other set, obtain the linear least squares fit equation in the form:
polar low-boiling compounds, such as dienes, can also be rspi 5 ~mi!~amti! 1 bi (9)
present in the analysis range. The oxygenates: acetone,
2-butanone, methyl ethyl ketone and acetaldehyde have very where:
close retention times to the oxygenates of interest in this rspi = response ratio for oxygenate/internal standard (y-
method. The user should be aware that changes in temperature axis)
and flow may cause these oxygenates to coelute with the mi = slope of linear equation for calibration curve
oxygenates of interest. On the other hand, the presence of the amti = amount ratio for methanol/internal standard (x -axis)
oxygenates mentioned above has not been detected in finished bi = y-axis intercept
gasoline. 10.9.3.1 An optimum calibration requires that the
10.9.2 Analyze the calibration standards and establish a y-intercept (bi) be kept at a minimum. A value greater than 1%
calibration curve for each oxygenate. Plot the response ratio of the slope should be cause for concern. If the value is
rspi as the y-axis versus the amount ratio amti as the x axis, See positive, the calibration solutions may need to be recalculated
Fig. 10 for an example plot. or prepared again. A negative value could also be explained by
poor calibration standards but also could be due to oxygenate
rspi 5 Ai / As (7)
adsorption in the system.
where: 10.9.4 Calculate the correlation coefficient r2 value for
Ai = area of component i calibration curve. The value r2 should be at least 0.99 or better.
As = area of internal standard The correlation r2 may be calculated directly by the data
amti 5 Wi / Ws (8) system or can be obtained by using plotting software.

11. Procedure
Wi = mass of component i in the calibration standard. 11.1 Preparation of Sample—Add 1 mL of the 1,2-DME
Ws = mass of internal standard in the calibration standard.
internal standard stock solution to 9.0000 g of sample. The

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FIG. 10 Example of Least Squares Fit Calibration for MTBE

concentration of internal standard is then 200 ppm. Record all Ai = area of oxygenate peak in sample,
masses to nearest 0.1 mg. Mix well the resulting solution for at As = area of internal standard added to sample,
least 1 min on a vortex or equivalent mixer. Transfer an aliquot bi = y-intercept of I from Eq 9,
of the solution into a glass gas chromatographic (GC) vial. Seal mi = slope of I from Eq 9, and
the GC vial with a TFE-fluorocarbon-lined septum. If the Ws = micrograms internal standard added {grams IS stock
sample is not immediately analyzed, store below 5°C. Do not * conc. of stock (µg/g)}.
store for more than 24 h. Then to determine the ppm levels of each oxygenate, apply
11.2 Chromatographic Analysis—Introduce a representa- the following equation:
tive aliquot of the sample, containing internal standard, into the Ci 5 Wi / Mt (11)
gas chromatograph, using the same technique and sample size
as used for the calibration analysis. Tables 1 and 2 contain
approximate suggested conditions. Synchronize sample intro- Ci = concentration of oxygenate, ppm,
duction with the start of recording and integrating devices. Wi = micrograms of oxygenate in the sample, µg, and
Obtain a chromatogram or integrated peak report, or both, Mt = total mass of solution, g.
which displays the retention times and integrated area of each 12.2 Error Determination – For the coelution referred to in
detected component. 10.9.1.3, some error will be associated with identification of a
11.3 Interpretation of Chromatogram—Compare the reten- single oxygenate while calibrating with an average RRF of a
tion times of sample to those of the calibration analysis to mixture of two or three oxygenates with different RRF’s. Refer
determine the identities of each oxygenate. to Table 4 for RRF values for each of the coeluting peaks and
the magnitude of the approximation when detecting a single
12. Calculations and Reporting component of the coelution.
12.1 Calculation of Oxygenate Concentration in Sample, 13. Quality Control Reference Material
ppm—After identifying an oxygenate, measure the areas of the 13.1 After the calibration has been completed, prepare two
peak and of the internal standard. From the least squares fit quality control check standard reference materials of selected
calibrations, Eq 9, calculate the absolute mass of the oxygenate oxygenates in automotive spark-ignition fuels or (preferred)
(Wi) in micrograms in the automotive spark-ignition fuel use any reference automotive spark-ignition fuel samples
samples using the response ratio (rspi) of the areas for the which have been used in round robins or cross check programs
oxygenate to that of the internal standard as follows in Eq 10. for which mean values of selected oxygenate concentrations
Wi 5@~Ai / As –bi! / mi] * Ws (10) have been determined. One concentration should be in the
lower concentration range, for example, 10 to 30 ppm, and
where: another in the upper concentration range, for example, 600 to
Wi = micrograms of oxygenate in the sample,
1000 ppm. Analyze the reference material as described in the

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sample preparation procedure. The oxygenate concentration cally spiked automotive spark-ignition fuel samples at varied
values obtained shall agree within 615 % for the 10 to 30 ppm concentration levels within the range of the method. All
reference material and 65 % relative for the 600 to 1000 ppm samples were analyzed by duplicate analysis. The Precision is
reference material. If the individual values are outside the shown in Table 5 and Example calculations are shown in Table
specified range, verify calibration and instrument parameters, 6. It is to be noted that the precision showed in Table 5 covers
the accuracy of the preparation of quality control reference only for the ranges indicated in Table 5. Precision should not be
material, etc. Do not analyze samples without meeting the used outside of the ranges specified in Table 5.
quality control specifications. 14.2 Repeatability (r)—The difference between successive
13.2 The check standards may be prepared by weighing results obtained by the same operator with the same apparatus
0.60 g of the oxygenate stock solution prepared in 10.3 and under constant operating conditions on identical test material
5.00 g neat ethanol in 94.4 g of an oxygenate-free automotive would in the long run, in the normal and correct operation of
spark-ignition fuel sample to prepare the upper end check the test method, exceed the values in Table 5 only in one case
standard. This corresponds to a 500 ppm oxygenate and 5% in twenty.
ethanol spiked sample. After shaking well, more dilute solu- 14.3 Reproducibility (R)—The difference between two
tions may be prepared by diluting gravimetrically aliquots of single and independent results obtained by different operators
the stock with additional oxygenate-free automotive spark- working in different laboratories on identical test materials
ignition fuel. Treat this sample like any other and add the would in the long run, exceed the values in Table 5 only in one
appropriate amount of internal standard before injection. case in twenty. When only a single test result is available, the
13.3 Analyze the quality control reference materials before Reproducibility Limit can be used to calculate a range (test
every batch of samples. Bracket the samples with the reference result 6 Reproducibility Limit) outside of which a second test
material. If the reference materials do not meet the specifica- result would expect to fall about one time in twenty. Repro-
tions in Section 13.1, the samples analyzed immediately ducibility results are shown in Table 5.
preceding the reference material are considered suspect and 14.4 Bias—No information can be presented on the bias of
should be reanalyzed. this procedure because an accepted reference material is not
available.
14. Precision and Bias
14.1 Precision—The precision of this test method was 15. Keywords
determined by statistical examination of a Round Robin study. 15.1 alcohols; automotive spark-ignition fuel; ethers; gas
This study involved five (5) laboratories and six (6) gravimetri- chromatography; oxygenates

TABLE 5 Repeatability and ReproducibilityA

Component Repeatability Reproducibility As per ILS
r (ppm wt/wt) R (ppm wt/wt) Range (ppm wt/wt)
ETBE 0.1503 * X ^ 0.8876 0.3221 *X ^ 0.8876 13 to 1759
MTBE 0.2548 * X ^ 0.8476 0.5809 * X ^ 0.8476 18 to 1717
DIPE 0.2678 * X ^ 0.7085 2.3323 * X ^ 0.4916 13 to 1703
TAME 0.2545 * X ^ 0.7467 0.3736 * X 0.7467 13 to 1842
Methanol 0.1272 * X ^ 0.9217 0.2045 * X ^ 0.9217 12 to 1881
n,i-Propanol 0.1173 * X ^ 0.9183 0.1720 * X ^ 0.9183 19 to 1904 ea
t,s,i-Butanol 0.003845 * X ^ 1.3463 0.008489 * X ^ 1.3463 19 to 1891 ea
n- Butanol 1.4747 * X ^ 0.4455 3.4596 * X ^ 0.4455 12 to 1952
t-Pentanol 0.4487 * X ^ 0.6306 0.9752 * X ^ 0.6306 13 to 1958
A
X = value obtained from analysis in ppm (wt/wt). Do not extrapolate outside the ranges noted.

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TABLE 6 Example Calculation of Precision for 100, 250 and 600 ppm (wt/wt) Oxygenates
100 ppm 250 ppm 600 ppm
r R r R r R
ETBE 9 19 20 43 44 94
MTBE 13 29 27 63 58 131
DIPE 7 22 13 35 25 54
TAME 8 12 16 23 30 44
Methanol 9 14 21 33 46 74
n,i-Propanol 8 12 19 27 42 61
t,s,i-Butanol 2 4 7 14 21 47
n- Butanol 11 27 17 40 25 60
t-Pentanol 8 18 15 32 25 55

APPENDIXES

(Nonmandatory Information)

X1. INDIVIDUAL OXYGENATE ANALYSIS

X1.1 This appendix details the procedure for analyzing than if the calibration was done using the complete cut time
individual oxygenates by using multiple cut times; one time for window of 0.5 min to 5.0 min. Refer to 10.9.1.
the oxygenate of interest and one for the internal standard. This
is based on the switching valve configuration. Alternative cut X1.4 Table X1.1 details the specific cut time windows for
times will have to be determined for instruments configured each oxygenate. Some of the windows do overlap due to partial
with a fluidic switch. resolution of the peaks from the pre-column using the condi-
tions set in Table 2. Figs. 5 and 6 shows the elution time of the
X1.2 This procedure allows for positive identification of oxygenates from the pre-column for the cut time determina-
coeluting peaks. Due to the boiling point elution characteristics tion.
of the apolar pre-column, the normal and iso-propanol as well X1.4.1 Fig. X1.1 shows a chromatogram of the analysis of
as the tert-, sec-, and iso-Butanol peaks elute at very different MTBE and 1,2-DME. The cut time windows used are from
times. Therefore specific cut time windows can be selected to Table X1.1 for the specific components in a sample containing
elute the suspected oxygenate. These specific windows can be 15% ethanol. Notice the small residual of the ethanol peak.
determined using the chromatogram of the calibration standard
run through the pre-column only.
TABLE X1.1 Cut Time Windows for Each Oxygenate
X1.2.1 An amount of ethanol will be seen in most analyses
NOTE—The first time is the Valve-ON position, and the second is the
depending on its concentration. This is due to the tailing effect
Valve-OFF position. These windows are approximate and may need
from the pre-column. Part of this tail will be seen with most cut adjustment depending on the instrument. If using a fluidic switch, times
time windows. If ethanol is to be determined in the percent may be different.
range, use the complete cut time established in Section 9. Component Window (min)

X1.3 If ethanol is present at concentration ranges higher ETBE 2.7 to 3.0

MTBE 1.9 to 2.2
than 15%, its elution into the PLOT column can be prevented DIPE 2.4 to 2.7
by opening a time window so that the ethanol is vented by TAME 3.8 to 4.4
introducing a cut time window that will exclude the ethanol Methanol 0.8 to 1.1
Ethanol 1.1 to 1.4
from entering the analytical column. This window can be set at i-Propanol 1.2 to 1.5
an approximate time of 1.1 to 1.4 min. This will significantly n-Propanol 1.7 to 2.0
reduce interferences with minor components present in the i-Butanol 2.6 to 2.9
s-Butanol 2.2 to 2.5
sample. t-Butanol 1.4 to 1.7
X1.3.1 Due to the lower amount of ethanol introduced into n-Butanol 3.3 to 3.6
t-Pentanol 2.8 to 3.2
the PLOT column using this procedure, the retention times of 1,2-DME 3.1 to 3.4
the ethers and methanol will elute ~0.2 min later than expected

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NOTE—Traces of other oxygenates due to overlapping windows.

FIG. X1.1 MTBE and Internal Standard Analysis Using Cut Time Windows from Table X1.1

X2. IDENTIFICATION OF OXYGENATE ANALYSIS

X2.1 During the ILS study it was noticed the difficulty in X2.2 These coelutions occur due to relative amount of
the separation and identification of the oxygenates eluting prior these three components ETBE, MTBE and DIPE occur a
to ethanol. Figs. X2.1-X2.4 represent cases, which clearly lead different relative quantities. This requires the observation that
to incorrect concentrations of these oxygenates. the peaks are not symmetrical indicating a coelution. This is

FIG. X2.1 Comparison of a Non-optimal and Optimal Resolution for a Sample Showing Incomplete Resolution between ETBE and MTBE

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FIG. X2.2 Comparison of a Non-optimal and Optimal Resolution for a Sample Showing Incomplete Resolution between ETBE and
MTBE, Having a Larger Concentration of DIPE

FIG. X2.3 Comparison of a Non-optimal and Optimal Resolution for a Sample Showing Incomplete Resolution between ETBE and
MTBE, Having a Larger Concentration of ETBE

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NOTE—Calibration Standard circa 90 ppm wt/wt each component.

FIG. X2.4 Elution pattern from WCOT /PLOT Columns for ETBE, MTBE, DIPE and TAME Using Conditions in Table 2

best by having a standard of these 3 peaks at the level of 20-90 (3) Recondition the column at 200°C for several hours.
ppm. (4) Verify that all lines that are used in the chromatography
are heated.
X2.3 The following factors should be considered when
optimizing the separation of these three components: (5) Check that there is a smooth transition in flows when
the valve is switched from in series to the PLOT column alone.
(1) Column flow
(2) Column Temperature (increase or decrease by 2 to 3°C) (6) Condition the apolar column.

X3. ADDITIONAL METHODOLOGY

X3.1 The “classic” Deans configuration also has been shown in Fig. X3.1. It allows for easy tuning of the cut-times.
suggested for this method as an additional technique. A The entire separation principle is the same, but allows for
pre-column with a fluidic switch that can send sample to either flexibility in the use of the configurations. It is to be noted that
a monitor column or an a analytical column, in single and dual this configuration was not used in determining the precision
detector configuration, which is similar to configuration C, is shown in Table 5.

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NOTE—Upper figure shows the bypass mode to the monitor detector. Lower figure shows the transfer mode of the oxygenates to the analytical column
and detector.
FIG. X3.1 Use of the Dean’s Switch Technique for the Analysis of Trace Oxygenates

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