ASTM D7524-10(2015)

Standard Test Method for Determination of Static Dissipater Additives (SDA) in Aviation Turbine Fuel and Middle Distillate Fuels—High Performance Liquid Chromatograph (HPLC) Method

SIGNIFICANCE AND USE
5.1 This test method will allow the determination of static dissipater additive in jet and middle distillate. These additives reduce the hazardous effects of static electricity generated by transfer and movement of jet and middle distillate fuels.
SCOPE
1.1 This test method covers the determination of static dissipater additive (SDA) content of aviation turbine fuel and middle distillate fuels.  
1.2 The precision of this test method has been established for aviation turbine fuel over the concentration range of 1 mg/L to 12 mg/L. Higher concentrations can be determined by dilution, but the precision of the test method will not apply.
Note 1: The SDA used to develop this test method was STADIS 4502 for aviation fuels and STADIS 450 and 4252 for middle distillates.  
1.3 The test method includes a procedure to concentrate the sulfonic acid component in the SDA prior to analysis.  
1.4 The test method only applies to SDAs that contain alkyl substituted sulfonic acid.  
1.5 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.  
1.6 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.

General Information

• Status: Historical
• Publication Date: 31-Mar-2015
• ICS: 75.160.20 - Liquid fuels
• Technical Committee: D02 - Petroleum Products, Liquid Fuels, and Lubricants
• Drafting Committee: D02.04.0C - Liquid Chromatography

Standards Content (Sample)

NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
Contact ASTM International (www.astm.org) for the latest information
Designation: D7524 − 10 (Reapproved 2015)
IP 568/08
Standard Test Method for
Determination of Static Dissipater Additives (SDA) in
Aviation Turbine Fuel and Middle Distillate Fuels—High
Performance Liquid Chromatograph (HPLC) Method
This standard is issued under the fixed designation D7524; 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 D4057Practice for Manual Sampling of Petroleum and
Petroleum Products
1.1 This test method covers the determination of static
D4177Practice for Automatic Sampling of Petroleum and
dissipater additive (SDA) content of aviation turbine fuel and
Petroleum Products
middle distillate fuels.
2.2 ISO Standards:
1.2 The precision of this test method has been established
EN ISO 3696 Water for Analytical Laboratory Use—
for aviation turbine fuel over the concentration range of
Specifications and Test Methods
1mg⁄Lto 12mg⁄L. Higher concentrations can be determined
2.3 Energy Institute Standards:
by dilution, but the precision of the test method will not apply.
IP 568/08Determination of the Static Dissipater Additives
NOTE 1—The SDAused to develop this test method was STADIS 450
2 (SDA) in Aviation Turbine Fuel and Middle Distillate
for aviation fuels and STADIS 450 and 425 for middle distillates.
Fuels—HPLC Method
1.3 The test method includes a procedure to concentrate the
sulfonic acid component in the SDA prior to analysis.
3. Terminology
1.4 ThetestmethodonlyappliestoSDAsthatcontainalkyl
3.1 Definitions:
substituted sulfonic acid.
3.1.1 middle distillate fuels, n—generic refinery/supplier
term that usually denotes a fuel primarily intended for use in
1.5 The values stated in SI units are to be regarded as
compression ignition/diesel engine applications, and also in
standard. No other units of measurement are included in this
non-aviation gas turbine engines and other non-automotive
standard.
applications such as a burner fuel.
1.6 This standard does not purport to address all of the
safety concerns, if any, associated with its use. It is the 3.2 Definitions of Terms Specific to This Standard:
responsibility of the user of this standard to establish appro- 3.2.1 aviation turbine fuel, n—fuel used for powering jet
priate safety and health practices and determine the applica- and turbo-prop engine aircraft.
bility of regulatory limitations prior to use.
3.2.2 conductivity improver additive, n—materialaddedtoa
fuel in very small amounts to increase its electrical conductiv-
2. Referenced Documents
ity and thereby reduce relaxation time.
3.2.2.1 Discussion—Conductivity improver additives are
2.1 ASTM Standards:
also known as static dissipater additives (SDAs) or antistatic
additives.
This test method is under the jurisdiction of ASTM Committee D02 on
4. Summary of Test Method
Petroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility of
Subcommittee D02.04.0C on Liquid Chromatography.
4.1 A solid phase extraction procedure is used to concen-
Current edition approved April 1, 2015. Published May 2015. Originally
tratethesulfonicacidcomponentofSDApresentinanaviation
approved in 2010. Last previous edition approved in 2010 as D7524–10.
turbinefuelormiddledistillatefuelsamplepriortoanalysis.A
DOI:10.1520/D7524-10R15.
Stadis 450 and 425 are registered trademarks marketed by Innospec, Inc.,
Innospec Manufacturing Park, Oil Sites Road, Ellesmere Port, Cheshire Ch65 4EY,
UK. Available from International Organization for Standardization (ISO), 1, ch. de
For referenced ASTM standards, visit the ASTM website, www.astm.org, or la Voie-Creuse, Case postale 56, CH-1211, Geneva 20, Switzerland, http://
contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM www.iso.ch.
Standards volume information, refer to the standard’s Document Summary page on Available from Energy Institute, 61 New Cavendish St., London, WIG 7AR,
the ASTM website. U.K., http://www.energyinst.org.uk.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D7524 − 10 (2015)
fixed volume of the concentrated test fraction is injected into a size, 250 mm × 4.6 mm ID is suitable, provided that it meets
calibrated high performance liquid chromatograph.An analyti- the resolution requirements specified in 9.3.
cal column is used to separate the sample components of the
6.6 HPLC Column Oven—Any suitable HPC column oven
test fraction by polarity.
block heating or air circulating) capable of maintaining a
4.2 The analytical column is attached to a liquid chroma- constant temperature of 61 °C within the range from 20 °C to
tography detector where the sulfonic acid components are 40 °C.
readily detected by UV absorption as they elute from the
NOTE 3—Alternative forms of temperature control are permitted, for
column. The electronic signal from the liquid chromatography
example, temperature-controlled laboratories.
detector is continually monitored by a chromatography data
6.7 Analytical Balance—Accurate to 60.0001 g.
system. The amplitudes of the signal (peak area) from the
6.8 Solid Phase Extraction (SPE) Columns Reservoirs —
sulfonic acids are compared with those obtained from previ-
Amino bonded silica, 6500 mg (A) or 100 mg (B) capacity.
ously measured calibration standards in order to calculate the
6.8.1 Reservoirs with Connectors—Approximately 60 mL
percent m/V SDA present in the sample.
capacity and connectors.
4.3 ThetestmethodonlyappliestoSDAsthatcontainalkyl
6.9 Solid Phase Extraction Vacuum Manifold—Optional.
substituted sulfonic acids.
6.10 Volumetric Flasks—ClassA,of2mL,5mL,10mL,25
5. Significance and Use
mL, and 100 mL capacity.
5.1 This test method will allow the determination of static
6.11 Graduated Pipette—Class A, of 1 mL, 2 mL, 10 mL,
dissipater additive in jet and middle distillate. These additives
and 50 mL capacity. Capable of delivering volumes of the
reduce the hazardous effects of static electricity generated by
range 0.5 mL to 4.0 mL with an accuracy of 60.0005 mL.
transfer and movement of jet and middle distillate fuels.
6.12 Measuring Cylinder—50 mL and 500 mL capacity.
6. Apparatus 6.13 pH meter.
6.1 High Performance Liquid Chromatograph (HPLC)—
7. Reagents and Materials
Any HPLC capable of pumping an isocratic mobile phase at
7.1 Dinonylnaphthalene Sulfonic Acid (DINNSA)—50%
flow rates between 0.1mL⁄min and 1.5mL⁄min, with a
(m/m) solution in heptane.
precision better than 0.5% and a pulsation of < 1% full scale
deflection under the test method conditions.
7.2 Dodecylbenzene Sulfonic Acid (DDBSA)—70% (m/m)
solution in 2-propanol.
6.2 Variable Wavelength Ultraviolet Photometric Detector
or Photometric DiodeArray Detector—Capableofoperationat
7.3 Tetrahydrofuran—HPLC grade. (Warning—HPLC
225nm and 234nm. grade tetrahydrofuran does not contain inhibitor, hence explo-
sive peroxides may form. Highly flammable and may cause
6.3 Manual or Automatic Sample Injection Valve—Capable
irritation by inhalation, ingestion or skin contact.)
of injecting 10 µL to 25 µL, using either partial or full loop
mode, with a repeatability 61%.
7.4 Hydrochloric Acid—37 %.
6.3.1 An equal and constant volume of the calibration and
7.5 Methanol—HPLC grade. (Warning— Methanol is
sample solutions is injected into the chromatograph. Both
highly flammable and toxic by inhalation, ingestion or skin
manual and automatic sample injection systems (using either
contact.)
complete or partial filling of the sample loop) will, when used
7.6 Methanolic Hydrochloric Acid—Mix approximately 1
correctly, meet the repeatability requirements specified in 6.3.
mLof hydrochloric acid (see 7.4) with approximately 9 mLof
NOTE 2—When using the partial loop-filling mode, it is recommended
methanol (see 7.5).
that the injection volume should be less than half the total loop volume.
Forcompletefillingoftheloop,bestresultsareobtainedbyoverfillingthe 7.7 Orthophosphoric Acid.
loop at least six times.
7.8 Sodium Hydroxide Pellets.
6.4 Chromatography Data System—Anydatasystemcanbe
7.9 Sodium Hydroxide Solution—Approximately 1 M. Dis-
used,provideditiscompatiblewiththeliquidchromatography
solve approximately4gof sodium hydroxide (see 7.8)in
detector, has a minimum sampling rate of 1 Hz, and is able to
approximately 100 mL of water.
measure peak areas and retention times and perform post-run
7.10 Buffered Phosphoric Acid—Add approximately 2 mL
data processing such as baseline correction and re-integration.
6 of orthophosphoric acid (see 7.7) to approximately 1l mL of
6.5 Analytical Column —Any stainless steel HPLC column
water and buffer to 2.5 pH using sodium hydroxide solution
packed with C alkyl-bonded reversed-phase, 5 µm particle
(see 7.9).
7.11 Isohexane—HPLC grade. (Warning— Isohexane is
highly flammable, and may cause irritation by inhalation,
The sole source of supply of the apparatus known to the committee at this time
is Waters Corp. 34 Maple St., Milford, MA 01757. If you are aware of alternative ingestion or skin contact.)
suppliers, please provide this information to ASTM International Headquarters.
7.12 Solid Phase Extraction (SPE) Columns and
Your comments will receive careful consideration at a meeting of the responsible
technical committee, which you may attend. Cartridges—Amino-bonded silica, 500 mg and 100 mg.
D7524 − 10 (2015)
TABLE 1 SPE Sample, Wash, and Elution Volumes
7.13 Mobile Phase—Mix approximately 400 mL methanol
(see 7.5), approximately 400 mL THF (see 7.3), and approxi- 500 mg 100 mg
SPE Column SPE Column
mately 50 mL of buffered phosphoric acid (see 7.10).
Sample volume 50 mL 10 mL
7.14 Nitrogen—Optional.
Isohexane/heptane wash 2 mL × 5 mL 2 mL × 2 mL
Methanol wash 5 mL 2 mL
NOTE 4—It is recommended practice to degas HPLC mobile phase
DINNSA/DDBSA eluate 5 mL 2 mL
before use; this can be done conveniently, on-line or off-line, by helium
sparging,vacuumdegassing,orultrasonicagitation.Afailuretodegasthe
mobile phase may lead to negative peaks.
7.15 Calibration Stock Solutions—Accurately weigh, to the
nearest 0.0001 g, between 0.078 g and 0.082 g of DINNSA columnundergravityorvacuumataflowrateof2mL⁄minor
solution (7.1) into a 100 mL volumetric flask and make up to
less. Discard the eluate.
the mark with heptane or mobile phase (7.13). Accurately
9.3 After all the fuel has eluted from the SPE column, rinse
weigh, to the nearest 0.0001 g, between 0.028 g to 0.032 g of
thereservoirandSPEadsorbentwithportionsofisohexane(or
DDBSA solution (7.2) into a 100 mL volumetric flask and
heptane) and then methanol, discarding the eluate (see Table
make up to the mark with heptane or mobile phase (7.13).
1).
7.16 Calibration Standards—From the calibration stock
9.4 Elute the sulfonic acid (DINNSAor DDBSA) from the
solutions (7.15), prepare a set of five calibration standards in
100mg or 500mg SPE column using approximately 2mL or
the mobile phase (7.13) to cover the concentration ranges
5mL of mobile phase (7.13), respectively, and collect the
indicated in the table:
eluate in a 2mLor 5mLvolumetric flask (6.10), making up to
SPE Column Size DINNSA DDBSA
the mark with mobile phase (7.13) if necessary. Replace
500 mg 0.8 mg/mL to 16 0.7 mg ⁄mL to 8.5
stopper in volumetric flask and shake well.
mg/mL mg/mL
100 mg 0.32 mg/mL to 9 0.35 mg ⁄mL to
9.5 Sample and eluent volumes are summarized in Table 1.
mg/mL 4.5 mg ⁄mL
NOTE 5—Asuggested procedure to prepare these standards is given in
10. Preparation of Apparatus
Annex A1.
10.1 Set up the pump, injector, detector, and data system
7.17 Calibration Check Solutions—2.0mg⁄L DINNSAand
according to the manufacturer’s instructions. Set the UV
2.8mg⁄L DBSA.
detector to 234nm for DINNSA and 225nm for DDBSA.
7.17.1 Prepare a 500mg⁄LDINNSAsolution by accurately
10.2 InstalltheHPLCcolumnandsetthemobilephaseflow
weighing, to the nearest 0.0001g, about 0.05g DINNSA(7.1)
rate to 0.5mL⁄min.
into a 50mLvolumetric flask and making up to the mark with
heptane. Pipette 1mLof this solution into a 25mLvolumetric
NOTE 6—Set the temperature of the column oven, if used, to at least
flask and make up to the mark with heptane (20mg⁄L
10°C above ambient, for example, 40°C.
DINNSA solution). Pipette 1mL of the 20mg⁄L DINNSA
10.3 When operating conditions are steady, inject a fixed
solution into a 10mLvolumetric flask and make up to volume
volume (10µL to 25µL) of the middle calibration standard
with mobile phase (7.13) to give a 2.0mg⁄L check solution.
(7.16),andensurethechromatogramresemblesthoseshownin
7.17.2 Prepare a 700mg⁄L DDBSA solution by accurately
Fig. 1 (DINNSA) or Fig. 2 (DDBSA).
weighing, to the nearest 0.0001g, 0.05g DDBSA (7.2) into a
NOTE 7—The sulfonic acid peak around 4min may exhibit some
50mL volumetric flask and making up to the mark with
broadening due to the presence of isomers but no fine structure.
heptane. Pipette 1mLof this solution into a 25mLvolumetric
NOTE 8—Small adjustments in the buffered phosphoric acid content of
flaskandmakeuptothemarkwithheptane(28mg⁄LDDBSA
themobilephasemayimprovethechromatographicprofileofthesulfonic
solution). Pipette 1mL of the 28 mg/L DDBSA solution into
acid.
a 10mL volumetric flask and make up to volume with mobile
10.4 Inject a fixed volume (10µL to 25µL) of the lowest
phase (7.13) to give a 2.8mg⁄L check solution.
concentration calibration standard (7.16) to check system
7.18 Water—Grade 3 of EN ISO 3696. sensitivity.Thedetectorshallhaveasignaltonoiseratio(S/N)
greater than 10 for the lowest concentration calibration stan-
8. Sampling dard; increase the injection volume if necessary.
8.1 Use only representative samples obtained as described
10.5 Inject the same volume (10µL to 25µL) of middle
in Practice D4057 or D4177, unless otherwise specified. calibration standard (7.16) five times to check system repeat-
ability (less than 1%).
9. Sample Preparation
10.6 Inject the same volume (10µLto 25µL) of all calibra-
9.1 Clamp the SPE column, 6.8(A) or 6.8(B), vertically or tion standards (7.16) to check system linearity (correlation
attach to a vacuum manifold if used.Add a 60mLreservoir to co-efficient greater than 0.995).
the500mgSPEcolumn(6.8(A))usingaconnector(6.8.1);the
10.7 Inject the same (10µL to 25 µL) of the highest
100mg SPE column has an integral reservoir.
concentration standard (7.16) followed by blank (mobile
9.2 Withapipette,transferthetestspecimen(seeTable1)to phase) injection to check for analyte carryover (less than 0.05
the SPE reservoir and allow the fuel to percolate through the %).
D752
...

This document is not an ASTM standard and is intended only to provide the user of an ASTM standard an indication of what changes have been made to the previous version. Because
it may not be technically possible to adequately depict all changes accurately, ASTM recommends that users consult prior editions as appropriate. In all cases only the current version
of the standard as published by ASTM is to be considered the official document.
Designation: D7524 − 10 D7524 − 10 (Reapproved 2015)
IP 568/08
Standard Test Method for
Determination of Static Dissipater Additives (SDA) in
Aviation Turbine Fuel and Middle Distillate Fuels—High
Performance Liquid Chromatograph (HPLC) Method
This standard is issued under the fixed designation D7524; 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
1.1 This test method covers the determination of static dissipater additive (SDA) content of aviation turbine fuel and middle
distillate fuels.
1.2 The precision of this test method has been established for aviation turbine fuel over the concentration range of 11 mg ⁄L to
12 mg ⁄L. Higher concentrations can be determined by dilution, but the precision of the test method will not apply.
2 2
NOTE 1—The SDA used to develop this test method was STADIS 450 for aviation fuels and STADIS 450 and 425 for middle distillates.
1.3 The test method includes a procedure to concentrate the sulfonic acid component in the SDA prior to analysis.
1.4 The test method only applies to SDAs that contain alkyl substituted sulfonic acid.
1.5 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
1.6 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility
of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory
limitations prior to use.
2. Referenced Documents
2.1 ASTM Standards:
D4057 Practice for Manual Sampling of Petroleum and Petroleum Products
D4177 Practice for Automatic Sampling of Petroleum and Petroleum Products
2.2 ISO Standards:
EN ISO 3696 Water for analytical laboratory use—Specifications and test methodsAnalytical Laboratory Use—Specifications
and Test Methods
2.3 Energy Institute Standards:
IP 568/08 Determination of the static dissipater additivesStatic Dissipater Additives (SDA) in aviation turbine fuel and middle
distillate fuels—HPLC methodAviation Turbine Fuel and Middle Distillate Fuels—HPLC Method
3. Terminology
3.1 Definitions:
3.1.1 middle distillate fuels, n—generic refinery/supplier term that usually denotes a fuel primarily intended for use in
compression ignition/diesel engine applications, and also in non-aviation gas turbine engines and other non-automotive
applications such as a burner fuel.
This test method is under the jurisdiction of ASTM Committee D02 on Petroleum Products Products, Liquid Fuels, and Lubricants and is the direct responsibility of
Subcommittee D02.04.0C on Liquid Chromatography.
Current edition approved Feb. 15, 2010April 1, 2015. Published April 2010May 2015. DOI:10.1520/D7524–10.Originally approved in 2010. Last previous edition
approved in 2010 as D7524 – 10. DOI:10.1520/D7524-10R15.
Stadis 450 and 425 are registered trademarks marketed by Innospec, Inc., Innospec Manufacturing Park, Oil Sites Road, Ellesmere Port, Cheshire Ch65 4EY, UK.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM Standards
volume information, refer to the standard’s Document Summary page on the ASTM website.
Available from International Organization for Standardization (ISO), 1, ch. de la Voie-Creuse, Case postale 56, CH-1211, Geneva 20, Switzerland, http://www.iso.ch.
Available from Energy Institute, 61 New Cavendish St., London, WIG 7AR, U.K., http://www.energyinst.org.uk.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D7524 − 10 (2015)
3.2 Definitions of Terms Specific to This Standard:
3.2.1 aviation turbine fuel, n—fuel used for powering jet and turbo-prop engine aircraft.
3.2.2 conductivity improver additive, n—material added to a fuel in very small amounts to increase its electrical conductivity
and thereby reduce relaxation time.
3.2.2.1 Discussion—
Conductivity improver additives are also known as static dissipater additives (SDAs) or antistatic additives.
4. Summary of Test Method
4.1 A solid phase extraction procedure is used to concentrate the sulfonic acid component of SDA present in an aviation turbine
fuel or middle distillate fuel sample prior to analysis. A fixed volume of the concentrated test fraction is injected into a calibrated
high performance liquid chromatograph. An analytical column is used to separate the sample components of the test fraction by
polarity.
4.2 The analytical column is attached to a liquid chromatography detector where the sulfonic acid components are readily
detected by UV absorption as they elute from the column. The electronic signal from the liquid chromatography detector is
continually monitored by a chromatography data system. The amplitudes of the signal (peak area) from the sulfonic acids are
compared with those obtained from previously measured calibration standards in order to calculate the percent m/V SDA present
in the sample.
4.3 The test method only applies to SDAs that contain alkyl substituted sulfonic acids.
5. Significance and Use
5.1 This test method will allow the determination of static dissipater additive in jet and middle distillate. These additives reduce
the hazardous effects of static electricity generated by transfer and movement of jet and middle distillate fuels.
6. Apparatus
6.1 High Performance Liquid Chromatograph (HPLC)—Any HPLC capable of pumping an isocratic mobile phase at flow rates
between 0.10.1 mL ⁄min and 1.51.5 mL ⁄ mL/min, min, with a precision better than 0.5%0.5 % and a pulsation of < 1%1 % full
scale deflection under the test method conditions.
6.2 Variable Wavelength Ultraviolet Photometric Detector or Photometric Diode Array Detector—Capable of operation at
225225 nm and 234 nm.234 nm.
6.3 Manual or Automatic Sample Injection Valve—Capable of injecting 10 μL to 25 μL, using either partial or full loop mode,
with a repeatability 61 %.
6.3.1 An equal and constant volume of the calibration and sample solutions is injected into the chromatograph. Both manual
and automatic sample injection systems (using either complete or partial filling of the sample loop) will, when used correctly, meet
the repeatability requirements specified in 6.3.
NOTE 2—When using the partial loop-filling mode, it is recommended that the injection volume should be less than half the total loop volume. For
complete filling of the loop, best results are obtained by overfilling the loop at least six times.
6.4 Chromatography Data System—Any data system can be used, provided it is compatible with the liquid chromatography
detector, has a minimum sampling rate of 1 Hz, and is able to measure peak areas and retention times and perform post-run data
processing such as baseline correction and re-integration.
6.5 Analytical Column —Any stainless steel HPLC column packed with C alkyl-bonded reversed-phase, 5 μm particle size,
250 mm × 4.6 mm ID is suitable, provided that it meets the resolution requirements specified in 9.3.
6.6 HPLC Column Oven—Any suitable HPC column oven block heating or air circulating) capable of maintaining a constant
temperature of 61°C 61 °C within the range from 20 °C to 40°C.40 °C.
NOTE 3—Alternative forms of temperature control are permitted, for example, temperature-controlled laboratories.
6.7 Analytical Balance—Accurate to 60.0001 g.
6.8 Solid Phase Extraction (SPE) Columns Reservoirs —Amino bonded silica, 6500 mg (A) or 100 mg (B) capacity.
6.8.1 Reservoirs with Connectors—Approximately 60 mL capacity and connectors.
6.9 Solid Phase Extraction Vacuum Manifold—Optional.
The sole source of supply of the apparatus known to the committee at this time is Waters Corp. 34 Maple St., Milford, MA 01757. If you are aware of alternative suppliers,
please provide this information to ASTM International Headquarters. Your comments will receive careful consideration at a meeting of the responsible technical committee,
which you may attend.
D7524 − 10 (2015)
6.10 Volumetric Flasks—Class A, of 2 mL, 5 mL, 10 mL, 25 mL, 25 mL, and 100 mL capacity.
6.11 Graduated Pipette—Class A, of 1 mL, 2 mL, 10 mL, and 50 mL capacity. Capable of delivering volumes of the range 0.5
mL to 4.0 mL with an accuracy of 60.0005 mL.
6.12 Measuring Cylinder—50 mL and 500 mL capacity.
6.13 pH meter.
7. Reagents and Materials
7.1 Dinonylnaphthalene Sulfonic Acid (DINNSA)—50 % (m/m) solution in heptane.
7.2 Dodecylbenzene Sulfonic Acid (DDBSA)—70 % (m/m) solution in 2-propanol.
7.3 Tetrahydrofuran—HPLC grade. (Warning—HPLC grade tetrahydrofuran does not contain inhibitor, hence explosive
peroxides may form. Highly flammable and may cause irritation by inhalation, ingestion or skin contact.)
7.4 Hydrochloric Acid—37%.37 %.
7.5 Methanol—HPLC grade. (Warning— Methanol is highly flammable and toxic by inhalation, ingestion or skin contact.)
7.6 Methanolic Hydrochloric Acid—Mix approximately 1 mL 1 mL of hydrochloric acid (see 7.4) with approximately 9 mL of
methanol (see 7.5).
7.7 Orthophosphoric Acid.
7.8 Sodium Hydroxide Pellets.
7.9 Sodium Hydroxide Solution—Approximately 1M. 1 M. Dissolve approximately 4 g of sodium hydroxide (see 7.8) in
approximately 100 mL of water.
7.10 Buffered Phosphoric Acid—Add approximately 2 mL of orthophosphoric acid (see 7.7) to approximately 1l mL of water
and buffer to 2.5 pH using sodium hydroxide solution (see 7.9).
7.11 Isohexane—HPLC grade. (Warning— Isohexane is highly flammable, and may cause irritation by inhalation, ingestion or
skin contact.)
7.12 Solid Phase Extraction (SPE) Columns and Cartridges—Amino-bonded silica, 500 mg and 100 mg.
7.13 Mobile Phase—Mix approximately 400 mL methanol (see 7.5), approximately 400 mL THF (see 7.3), and approximately
50 mL of buffered phosphoric acid (see 7.10).
7.14 Nitrogen—Optional.
NOTE 4—It is recommended practice to degas HPLC mobile phase before use; this can be done conveniently, on-line or off-line, by helium sparging,
vacuum degassing, or ultrasonic agitation. A failure to degas the mobile phase may lead to negative peaks.
7.15 Calibration Stock Solutions—Accurately weigh, to the nearest 0.0001 g, between 0.078 g and 0.082 g of DINNSA solution
(7.1) into a 100 mL volumetric flask and make up to the mark with heptane or mobile phase (7.13). Accurately weigh, to the nearest
0.0001 g, between 0.028 g to 0.032 g of DDBSA solution (7.2) into a 100 mL volumetric flask and make up to the mark with
heptane or mobile phase (7.13).
7.16 Calibration Standards—From the calibration stock solutions (7.15), prepare a set of five calibration standards in the mobile
phase (7.13) to cover the concentration ranges indicated in the table:
SPE Column Size DINNSA DDBSA
500 mg 0.8 to 16 mg/mL 0.7 to 8.5 mg/mL
500 mg 0.8 mg/mL to 16 0.7 mg ⁄ mL to 8.5
mg/mL mg/mL
100 mg 0.32 to 9 mg/mL 0.35 to 4.5 mg/mL
100 mg 0.32 mg/mL to 9 0.35 mg ⁄ mL to
mg/mL 4.5 mg ⁄ mL
NOTE 5—A suggested procedure to prepare these standards is given in Annex A1.
7.17 Calibration Check Solutions—2.02.0 mg ⁄ mg/L L DINNSA and 2.82.8 mg ⁄ mg/L L DBSA.
7.17.1 Prepare a 500500 mg ⁄ mg/L L DINNSA solution by accurately weighing, to the nearest 0.0001 g, about 0.05 g 0.0001 g,
about 0.05 g DINNSA (7.1) into a 50 mL 50 mL volumetric flask and making up to the mark with heptane. Pipette 1 mL 1 mL
of this solution into a 25 mL 25 mL volumetric flask and make up to the mark with heptane (20(20 mg ⁄ mg/L L DINNSA solution).
Pipette 1 mL 1 mL of the 2020 mg ⁄ mg/L L DINNSA solution into a 10 mL 10 mL volumetric flask and make up to volume with
mobile phase (7.13) to give a 2.02.0 mg ⁄ mg/L L check solution.
7.17.2 Prepare a 700700 mg ⁄ mg/L L DDBSA solution by accurately weighing, to the nearest 0.0001 g, 0.05 g 0.0001 g, 0.05 g
DDBSA (7.2) into a 50 mL 50 mL volumetric flask and making up to the mark with heptane. Pipette 1 mL 1 mL of this solution
into a 25 mL 25 mL volumetric flask and make up to the mark with heptane (28(28 mg ⁄ mg/L L DDBSA solution). Pipette 1 mL
D7524 − 10 (2015)
TABLE 1 SPE Sample, Wash, and Elution Volumes
500 mg 100 mg
SPE Column SPE Column
Sample volume 50 mL 10 mL
Isohexane/heptane 2 × 5 mL 2 × 2 mL
wash
Methanol wash 5 mL 2 mL
DINNSA/DDBSA 5 mL 2 mL
eluate
TABLE 1 SPE Sample, Wash, and Elution Volumes
500 mg 100 mg
SPE Column SPE Column
Sample volume 50 mL 10 mL
Isohexane/heptane wash 2 mL × 5 mL 2 mL × 2 mL
Methanol wash 5 mL 2 mL
DINNSA/DDBSA eluate 5 mL 2 mL
1 mL of the 2828 mg/L DDBSA solution into a 10 mL 10 mL volumetric flask and make up to volume with mobile phase (7.13)
to give a 2.82.8 mg ⁄ mg/L L check solution.
7.18 Water—Grade 3 of EN ISO 3696.
8. Sampling
8.1 Use only representative samples obtained as described in Practice D4057 or D4177, unless otherwise specified.
9. Sample Preparation
9.1 Clamp the SPE column, 6.8(A) or 6.8(B), vertically or attach to a vacuum manifold if used. Add a 60 mL 60 mL reservoir
to the 500 mg 500 mg SPE column (6.8(A)) using a connector (6.8.1); the 100 mg 100 mg SPE column has an integral reservoir.
9.2 With a pipette, transfer the test specimen (see Table 1) to the SPE reservoir and allow the fuel to percolate through the
column under gravity or vacuum at a flow rate of 22 mL ⁄ mL/min min or less. Discard the eluate.
9.3 After all the fuel has eluted from the SPE column, rinse the reservoir and SPE adsorbent with portions of isohexane (or
heptane) and then methanol, discarding the eluate (see Table 1).
9.4 Elute the sulfonic acid (DINNSA or DDBSA) from the 100100 mg or 500 mg 500 mg SPE column using approximately
22 mL or 5 mL 5 mL of mobile phase (7.13), respectively, and collect the eluate in a 22 mL or 5 mL 5 mL volumetric flask (6.10),
making up to the mark with mobile phase (7.13) if necessary. Replace stopper in volumetric flask and shake well.
9.5 Sample and eluent volumes are summarized in Table 1.
10. Preparation of Apparatus
10.1 Set up the pump, injector, detector, and data system according to the manufacturer’s instructions. Set the UV detector to
234 nm 234 nm for DINNSA and 225 nm 225 nm for DDBSA.
10.2 Install the HPLC column and set the mobile phase flow rate to 0.5 0.5 mL mL/min.⁄mi
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